Fungicidal Mixtures Based on Azolopyrimidinylamines

ABSTRACT

Fungicidal mixtures comprising, as active components,
     1) azolopyrimidinylamines of the formula I,   

     
       
         
         
             
             
         
       
         
         
           
             in which the substituents are as defined in the description
 
and
 
           
         
         2) at least one active compound II selected from the following groups:
       azoles, strobilurins, carboxamides, heterocylic compounds, carbamates and other active compounds selected from the group consisting of guanidines, antibiotics, sulfur-containing heterocyclyl compounds, organophosphorus compounds, organochlorine compounds, inorganic active compounds, growth retardants and cyflufenamid, cymoxanil, dimethirimol, ethirimol, furalaxyl, metrafenone and spiroxamine;
 
in a synergistically effective amount.
   
     
       
    
     Methods for controlling harmful fungi using mixtures of the compound I with active compounds II and the use of the compound I with active compounds II for preparing such mixtures, and also compositions comprising these mixtures.

This application is a Divisional of U.S. application Ser. No. 11/996,608, filed Jan. 24, 2008, which is a National Stage application of International Application No. PCT/EP2006/064463 filed Jul. 20, 2006, the entire contents of which is hereby incorporated herein by reference. This application also claims the benefit under 35 U.S.C. §119 of German Patent Application No. 102005035688.5, filed Jul. 27, 2005.

DESCRIPTION

The present invention relates to fungicidal mixtures comprising, as active components,

1) azolopyrimidinylamines of the formula I,

-   -   in which the substituents are as defined below:     -   R¹ is C₃-C₁₂-alkyl, C₂-C₁₂-alkenyl, C₅-C₁₂-alkoxyalkyl,         C₃-C₆-cycloalkyl, phenyl or phenyl-C₁-C₄-alkyl;     -   R² is C₁-C₁₂-alkyl, C₂-C₁₂-alkenyl, C₁-C₄-haloalkyl,         C₁-C₄-alkoxy-C₁-C₄-alkyl;         -   where the aliphatic chains in R¹ and/or R² may be             substituted by one to four identical or different groups             R^(a):         -   R^(a) is halogen, cyano, hydroxyl, mercapto, C₁-C₁₀-alkyl,             C₁-C₁₀-haloalkyl, C₃-C₈-cycloalkyl, C₂-C₁₀-alkenyl,             C₂-C₁₀-alkynyl, C₁-C₆-alkoxy, C₁-C₆-alkylthio,             C₁-C₆-alkoxy-C₁-C₆-alkyl or NR^(A)R^(B);             -   R^(A), R^(B) are hydrogen and C₁-C₆-alkyl;             -   where the cyclic groups in R¹ and/or R^(a) may be                 substituted by one to four groups R^(b):         -   R^(b) is halogen, cyano, hydroxyl, mercapto, nitro,             NR^(A)R^(B), C₁-C₁₀-alkyl, C₁-C₆-haloalkyl, C₂-C₆-alkenyl,             C₂-C₆-alkynyl or C₁-C₆-alkoxy;     -   R³ is hydrogen, halogen, cyano, NR^(A)R^(B), hydroxyl, mercapto,         C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₃-C₈-cycloalkyl, C₁-C₆-alkoxy,         C₁-C₆-alkylthio, C₃-C₈-cycloalkoxy, C₃-C₈-cycloalkylthio,         carboxyl, formyl, C₁-C₁₀-alkylcarbonyl, C₁-C₁₀-alkoxycarbonyl,         C₂-C₁₀-alkenyloxycarbonyl, C₂-C₁₀-alkynyloxycarbonyl, phenyl,         phenoxy, phenylthio, benzyloxy, benzylthio,         C₁-C₆-alkyl-S(O)_(m)—;         -   M is 0, 1 or 2;     -   A is CH or N;         and         2) at least one active compound II selected from the following         groups:     -   A) azoles, such as bitertanol, bromuconazole, cyproconazole,         difenoconazole, diniconazole, enilconazole, epoxiconazole,         fluquinconazole, fenbuconazole, flusilazole, flutriafol,         hexaconazole, imibenconazole, ipconazole, metconazole,         myclobutanil, penconazole, propiconazole, prothioconazole,         simeconazole, triadimefon, triadimenol, tebuconazole,         tetraconazole, triticonazole;         -   prochloraz, pefurazoate, imazalil, triflumizole, cyazofamid;         -   benomyl, carbendazim, thiabendazole, fuberidazole;         -   ethaboxam, etridiazole, hymexazole;     -   B) strobilurins, such as azoxystrobin, dimoxystrobin,         enestroburin, fluoxastrobin, kresoxim-methyl, metominostrobin,         orysastrobin, picoxystrobin, pyraclostrobin, trifloxystrobin, or         methyl         (2-chloro-5-[1-(3-methylbenzyl-oxyimino)ethyl]benzyl)carbamate,         methyl         (2-chloro-5-[1-(6-methylpyridin-2-yl-methoxyimino)ethyl]benzyl)carbamate,         methyl         2-(ortho-((2,5-di-methylphenyloxymethylene)phenyl)-3-methoxyacrylate;     -   C) carboxamides, such as carboxin, benalaxyl, boscalid,         fenhexamid, flutolanil, furametpyr, mepronil, metalaxyl,         mefenoxam, ofurace, oxadixyl, oxycarboxin, penthiopyrad,         thifluzamide, tiadinil,         N-(4′-bromobiphenyl-2-yl)-4-difluoromethyl-2-methylthiazole-5-carboxamide,         N-(4′-trifluoromethylbiphenyl-2-yl)-4-difluoromethyl-2-methylthiazole-5-carboxamide,         N-(4′-chloro-3′-fluorobiphenyl-2-yl)-4-difluoromethyl-2-methylthiazole-5-carboxamide,         N-(3′,4′-dichloro-4-fluorobiphenyl-2-yl)-3-difluoromethyl-1-methylpyrazole-4-carboxamide,         N-(3′,4′-dichloro-5-fluorobiphenyl-2-yl)-3-difluoromethyl-1-methylpyrazole-4-carboxamide;         -   3,4-dichloro-N-(2-cyanophenyl)isothiazol-5-carboxamide;             dimethomorph, flumorph;         -   flumetover, fluopicolide (picobenzamid), zoxamide;         -   carpropamid, diclocymet, mandipropamid;         -   N-(2-{4-[3-(4-chlorophenyl)prop-2-ynyloxy]-3-methoxyphenyl}ethyl)-2-methanesulfonylamino-3-methylbutyramide,             N-(2-{4-[3-(4-chlorophenyl)-prop-2-ynyloxy]-3-methoxyphenyl}ethyl)-2-ethanesulfonylamino-3-methylbutyramide;     -   D) heterocylic compounds, such as fluazinam, pyrifenox;         -   bupirimate, cyprodinil, fenarimol, ferimzone, mepanipyrim,             nuarimol, pyrimethanil;         -   triforine;         -   fenpiclonil, fludioxonil;         -   aldimorph, dodemorph, fenpropimorph, tridemorph;             fenpropidin, iprodione, procymidone, vinclozolin;         -   famoxadone, fenamidone, octhilinone, probenazole;         -   amisulbrom, anilazine, diclomezine, pyroquilon, proquinazid,             tricyclazole;         -   5-chloro-7-(4-methylpiperidin-1-yl)-6-(2,4,6-trifluorophenyl)-[1,2,4]triazolo[1,5-a]pyrimidine,         -   2-butoxy-6-iodo-3-propylchromen-4-one;         -   acibenzolar-5-methyl, captafol, captan, dazomet, folpet,             fenoxanil, quinoxyfen;             3-[5-(4-chlorophenyl)-2,3-dimethylisoxazolidin-3-yl]pyridine;     -   E) carbamates, such as mancozeb, maneb, metam, metiram, ferbam,         propineb, thiram, zineb, ziram;         -   diethofencarb, iprovalicarb, flubenthiavalicarb,             propamocarb;         -   methyl             3-(4-chlorophenyl)-3-(2-isopropoxycarbonylamino-3-methylbutyrylamino)propanoate;     -   and     -   F) other active compounds, such as         -   guanidines: dodine, iminoctadine, guazatine;         -   antibiotics: kasugamycin, streptomycin, polyoxine,             validamycin A;         -   nitrophenyl derivates: binapacryl, dinocap, dinobuton;         -   sulfur-containing heterocyclyl compounds: dithianon,             isoprothiolane;         -   organometal compounds: fentin salts, such as fentin-acetate;         -   organophosphorus compounds: edifenphos, iprobenfos, fosetyl,             fosetyl-aluminum, phosphorous acid and its salts,             pyrazophos, tolclofos-methyl;         -   organochlorine compounds: chlorothalonil, dichlofluanid,             flusulfamide, hexachlorobenzene, phthalide, pencycuron,             quintozene, thiophanate-methyl, tolylfluanid;         -   inorganic active compounds: Bordeaux mixture, copper             acetate, copper hydroxide, copper oxychloride, basic copper             sulfate, sulfur;         -   others: cyflufenamid, cymoxanil, dimethirimol, ethirimol,             furalaxyl, metrafenone and spiroxamine;         -   growth retardants: prohexadione and its salts,             trinexapac-ethyl, chlormequat, mepiquat-chloride and             diflufenzopyr;             in a synergistically effective amount.

Moreover, the invention relates to a method for controlling harmful fungi using mixtures of the compound I with active compounds II and to the use of the compound I with active compounds II for preparing such mixtures, and also to compositions comprising these mixtures.

The azolopyrimidin-7-ylamines of the formula I referred to above as component 1, their preparation and their action against harmful fungi are known from the literature (EP-A 71 792; EP-A 141 317; WO 03/009687; WO 05/087771; WO 05/087772; WO 05/087773; PCT/EP/05/002426; PCT/EP2006/050922; PCT/EP2006/060399.

The active compounds II mentioned above as component 2, their preparation and their action against harmful fungi are generally known (cf.: http://www.hclrss.demon.co.uk/index.html); they are commercially available.

-   bitertanol,     β-([1,1′-biphenyl]-4-yloxy)-α-(1,1-dimethylethyl)-1H-1,2,4-triazole-1-ethanol     (DE 23 24 020), -   bromuconazole,     1-[[4-bromo-2-(2,4-dichlorophenyl)tetrahydro-2-furanyl]methyl]-1H-1,2,4-triazole     (Proc. 1990 Br. Crop. Prot. Conf.—Pests Dis. Vol. 1, p. 459); -   cyproconazole,     2-(4-chlorophenyl)-3-cyclopropyl-[1,2,4]triazol-1-ylbutan-2-ol (U.S.     Pat. No. 4,664,696); -   difenoconazole,     1-{2-[2-chloro-4-(4-chlorophenoxy)phenyl]-4-methyl-[1,3]dioxolan-2-ylmethyl}-1H-[1,2,4]triazole     (GB-A 2 098 607); -   diniconazole,     (βE)-β-[(2,4-dichlorophenyl)methylene]-α-(1,1-dimethylethyl)-1H-1,2,4-triazole-1-ethanol     (Noyaku Kagaku, 1983, Vol. 8, p. 575); -   enilconazole (imazalil),     1-[2-(2,4-dichlorphenyl)-2-(2-propenyloxy)ethyl]-1H-imidazole     (Fruits, 1973, Vol. 28, p. 545); -   epoxiconazole,     (2RS,3SR)-1-[3-(2-chlorophenyl)-2,3-epoxy-2-(4-fluorophenyl)propyl]-1H-1,2,4-triazole     (EP-A 196 038); -   fluquinconazole,     3-(2,4-dichlorophenyl)-6-fluoro-2-[1,2,4]-triazol-1-yl-3H-quinazolin-4-one     (Proc. Br. Crop Prot. Conf.—Pests Dis., 5-3, 411 (1992)); -   fenbuconazole,     α-[2-(4-chlorophenyl)ethyl]-α-phenyl-1H-1,2,4-triazole-1-propanenitrile     (Proc. 1988 Br. Crop Prot. Conf.—Pests Dis. Vol. 1, p. 33); -   flusilazole,     1-{[bis-(4-fluorophenyl)methylsilanyl]methyl}-1H-[1,2,4]triazole     (Proc. Br. Crop Prot. Conf.—Pests Dis., 1, 413 (1984)); -   flutriafol,     α-(2-fluorophenyl)-α-(4-fluorophenyl)-1H-1,2,4-triazole-1-ethanol     (EP 15 756); -   hexaconazole, 2-(2,4-dichlorophenyl)-1-[1,2,4]triazol-1-ylhexan-2-ol     (CAS RN 79983-71-4); -   imibenconazole, (4-chlorophenyl)methyl     N-(2,4-dichlorophenyl)-1H-1,2,4-triazole-1-ethanimidothioate ((Proc.     1988 Br. Crop Prot. Conf.—Pests Dis. Vol. 2, p. 519), -   imidothioate ((Proc. 1988 Br. Crop Prot. Conf.—Pests Dis. Vol. 2, p.     519), -   ipconazole,     2-[(4-chlorophenyl)methyl]-5-(1-methylethyl)-1-(1H-1,2,4-triazol-1-yl-methyl)cyclopentanol     (EP 267 778), -   metconazole,     5-(4-chlorobenzyl)-2,2-dimethyl-1-[1,2,4]triazol-1-ylmethylcyclopentanol     (GB 857 383); -   myclobutanil,     2-(4-chlorophenyl)-2-[1,2,4]triazol-1-ylmethylpentanenitrile (CAS RN     88671-89-0); -   penconazole, 1-[2-(2,4-dichlorophenyl)pentyl]-1H-[1,2,4]triazole     (Pesticide Manual, 12th Ed. (2000), p. 712); -   propiconazole,     1-[[2-(2,4-dichlorophenyl)-4-propyl-1,3-dioxolan-2-yl]methyl]-1H-1,2,4-triazole     (BE 835 579); -   prothioconazole,     2-[2-(1-chlorocyclopropyl)-3-(2-chlorophenyl)-2-hydroxypropyl]-2,4-dihydro-[1,2,4]triazole-3-thione     (WO 96/16048); -   simeconazole,     α-(4-fluorophenyl)-α-[(trimethylsilyl)methyl]-1H-1,2,4-triazole-1-ethanol     [CAS RN 149508-90-7], -   triadimefon,     1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)-2-butanone; -   triadimenol,     β-(4-chlorophenoxy)-α-(1,1-dimethylethyl)-1H-1,2,4-triazole-1-ethanol; -   tebuconazole,     1-(4-chlorophenyl)-4,4-dimethyl-3-[1,2,4]triazol-1-ylmethylpentan-3-ol     (EP-A 40 345); -   tetraconazole,     1-[2-(2,4-dichlorophenyl)-3-(1,1,2,2-tetrafluoroethoxy)propyl]-1H-1,2,4-triazole     (EP 234 242); -   triticonazole,     (5E)-5-[(4-chlorophenyl)methylene]-2,2-dimethyl-1-(1H-1,2,4-triazol-1-ylmethyl)cyclopentanol     (FR 26 41 277); -   prochloraz,     N-{propyl-[2-(2,4,6-trichlorophenoxy)ethyl]}imidazole-1-carboxamide     (U.S. Pat. No. 3,991,071); -   pefurazoate, 4-pentenyl     2-[(2-furanylmethyl)(1H-imidazol-1-ylcarbonyl)amino]butanoate [CAS     RN 101903-30-4], -   triflumizole,     (4-chloro-2-trifluoromethylphenyl)-(2-propoxy-1-[1,2,4]triazol-1-ylethylidene)amine     (JP-A 79/119 462) -   cyazofamid,     4-chloro-2-cyano-N,N-dimethyl-5-(4-methylphenyl)-1H-imidazole-1-sulfonamide     (CAS RN 120116-88-3], -   benomyl, N-butyl-2-acetylaminobenzoimidazol-1-carboxamide (U.S. Pat.     No. 3,631,176); -   carbendazim, methyl (1H-benzoimidazol-2-yl)-carbamate (U.S. Pat. No.     3,657,443); -   thiabendazole, 2-(1,3-thiazol-4-yl)benzimidazole (U.S. Pat. No.     3,017,415), -   fuberidazole, 2-(2-furanyl)-1H-benzimidazole (DE 12 09 799), -   ethaboxam,     N-(cyano-2-thienylmethyl)-4-ethyl-2-(ethylamino)-5-thiazolcarboxamide     (EP-A 639 574), -   etridiazole, -   hymexazole, 5-methyl-1,2-oxazol-3-ol (JP 518249, JP 532202), -   azoxystrobin, methyl     2-{2-[6-(2-cyano-1-vinylpenta-1,3-dienyloxy)pyrimidin-4-yloxy]phenyl}-3-methoxyacrylate     (EP-A 382 375), -   dimoxystrobin,     (E)-2-(methoxyimino)-N-methyl-2-[α-(2,5-xylyloxy)-o-tolyl]acetamide     (EP-A 477 631); -   fluoxastrobin,     (E)-{2-[6-(2-chlorophenoxy)-5-fluoropyrimidin-4-yloxy]phenyl}(5,6-dihydro-1,4,2-dioxazin-3-yl)methanone     O-methyloxime (WO 97/27189); -   kresoxim-methyl, methyl     (E)-methoxyimino[α-(o-tolyloxy)-o-tolyl]acetate (EP-A 253 213);     metominostrobin,     (E)-2-(methoxyimino)-N-methyl-2-(2-phenoxyphenyl)acetamide (EP-A 398     692); -   orysastrobin,     (2E)-2-(methoxyimino)-2-{2-[(3E,5E,6E)-5-(methoxyimino)-4,6-dimethyl-2,8-dioxa-3,7-diazanona-3,6-dien-1-yl]phenyl}-N-methylacetamide     (WO 97/15552); -   picoxystrobin, methyl     3-methoxy-2-[2-(6-trifluoromethylpyridin-2-yloxymethyl)phenyl]acrylate     (EP-A 278 595); -   pyraclostrobin, methyl     N-{2-[1-(4-chlorophenyl)-1H-pyrazol-3-yloxymethyl]phenyl}(N-methoxy)carbamate     (WO-A 96/01256); -   trifloxystrobin, methyl     (E)-methoxyimino-{(E)-α-[1-(α,α,α-trifluoro-m-tolyl)ethylidene-aminooxy]-o-tolyl}acetate     (EP-A 460 575); -   carboxin, 5,6-dihydro-2-methyl-N-phenyl-1,4-oxathiin-3-carboxamide     (U.S. Pat. No. 3,249,499), -   benalaxyl, methyl N-(phenylacetyl)-N-(2,6-xylyl)-DL-alaninate (DE 29     03 612), -   boscalid, 2-chloro-N-(4′-chlorbiphenyl-2-yl)nicotinamide (EP-A 545     099); -   fenhexamid,     N-(2,3-dichloro-4-hydroxyphenyl)-1-methylcyclohexanecarboxamide     (Proc. Br. Crop Prot. Conf.—Pests Dis., 1998, Vol. 2, p. 327); -   flutolanil, α,α,α-trifluoro-3′-isopropoxy-o-toluanilide (JP     1104514), -   furametpyr,     5-chloro-N-(1,3-dihydro-1,1,3-trimethyl-4-isobenzofuranyl)-1,3-dimethyl-1H-pyrazole-4-carboxamide     [CAS RN 123572-88-3], -   mepronil, 3′-isopropoxy-o-toluanilide (U.S. Pat. No. 3,937,840), -   metalaxyl, methyl N-(methoxyacetyl)-N-(2,6-xylyl)-DL-alaninate (GB     15 00 581); -   mefenoxam, methyl     N-(2,6-dimethylphenyl)-N-(methoxyacetyl)-D-alaninate; -   ofurace, (RS)-α-(2-chloro-N-2,6-xylylacetamido)-γ-butyrolactone [CAS     RN 58810-48-3]; -   oxadixyl;     N-(2,6-dimethylphenyl)-2-methoxy-N-(2-oxo-3-oxazolidinyl)acetamide     (GB 20 58 059), -   oxycarboxin, 5,6-dihydro-2-methyl-1,4-oxathiin-3-carboxanilide     4,4-dioxide (U.S. Pat. No. 3,399,214), -   penthiopyrad,     N-[2-(1,3-dimethylbutyl)-3-thienyl]-1-methyl-3-(trifluoromethyl)-1H-pyrazole-4-carboxamide     (JP 10130268), -   thifluzamide,     N-[2,6-dibromo-4-(trifluoromethoxy)phenyl]-2-methyl-4-(trifluoromethyl)-5-thiazolecarboxamide; -   tiadinil, 3′-chloro-4,4′-dimethyl-1,2,3-thiadiazole-5-carboxanilide     [CAS RN 223580-51-6], -   dimethomorph,     3-(4-chlorophenyl)-3-(3,4-dimethoxyphenyl)-1-morpholin-4-ylpropenone     (EP-A 120 321); -   flumorph,     3-(4-fluorophenyl)-3-(3,4-dimethoxyphenyl)-1-morpholin-4-ylpropenone     (EP-A 860 438); -   flumetover,     2-(3,4-dimethoxyphenyl)-N-ethyl-α,α,α-trifluoro-N-methyl-p-toluamide     [AGROW No. 243, 22 (1995)], -   fluopicolide (picobenzamid),     2,6-dichloro-N-(3-chloro-5-trifluoromethylpyridin-2-ylmethyl)benzamide     (WO 99/42447); -   zoxamide,     (RS)-3,5-dichloro-N-(3-chloro-1-ethyl-1-methyl-2-oxopropyl)-p-toluamide     [CAS RN 156052-68-5]; -   carpropamid,     2,2-dichloro-N-[1-(4-chlorophenyl)ethyl]-1-ethyl-3-methylcyclopropane-carboxamide     [CAS RN 104030-54-8], -   diclocymet,     2-cyano-N-[(1R)-1-(2,4-dichlorophenyl)ethyl]-3,3-dimethyl     butanamide; -   mandipropamid,     (RS)-2-(4-chlorophenyl)-N-[3-methoxy-4-(prop-2-ynyloxy)phenethyl]-2-(prop-2-ynyloxy)acetamide     [CAS RN 374726-62-2]; -   fluazinam,     3-chloro-N-[3-chloro-2,6-dinitro-4-(trifluoromethyl)phenyl]-5-(trifluoromethyl)-2-pyridinamine     (The Pesticide Manual, publ. The British Crop Protection Council,     10th ed. (1995), p. 474); -   pyrifenox, 1-(2,4-dichlorophenyl)-2-(3-pyridinyl)ethanone     O-methyloxime (EP-A 49 854); -   bupirimate,     5-butyl-2-ethylamino-6-methylpyrimidin-4-yldimethylsulfamate [CAS RN     41483-43-6]; -   cyprodinil, (4-cyclopropyl-6-methylpyrimidin-2-yl)phenylamine (EP-A     310 550); -   fenarimol, (4-chlorophenyl)(2-chlorophenyl)pyrimidin-5-ylmethanol     (GB 12 18 623); -   ferimzone, (Z)-2′-methylacetophenone     4,6-dimethylpyrimidin-2-ylhydrazone [CAS RN 89269-64-7]; -   mepanipyrim, (4-methyl-6-prop-1-ynylpyrimidin-2-yl)phenylamine (EP-A     224 339); -   nuarimol, α-(2-chlorophenyl)-α-(4-fluorophenyl)-5-pyrimidinemethanol     (GB 12 18 623); -   pyrimethanil, 4,6-dimethylpyrimidin-2-ylphenylamine (DD-A 151 404); -   triforine,     N,N′-{piperazine-1,4-diylbis[(trichloromethyl)methylene]}diformamide     (DE 19 01 421); -   fenpiclonil, 4-(2,3-dichlorophenyl)-1H-pyrrole-3-carbonitrile (Proc.     1988 Br. Crop Prot. Conf.—Pests Dis., Vol. 1, p. 65); -   fludioxonil,     4-(2,2-difluorobenzo[1,3]dioxol-4-yl)-1H-pyrrole-3-carbonitrile (The     Pesticide Manual, publ. The British Crop Protection Council, 10th     ed. (1995), p. 482); -   aldimorph, 4-alkyl-2,5 (or 2,6)-dimethylmorpholine, comprising     65-75% of 2,6-dimethylmorpholine and 25-35% of     2,5-dimethylmorpholine, comprising more than 85% of 4-dodecyl-2,5     (or 2,6)-dimethylmorpholine, where “alkyl” may also include octyl,     decyl, tetradecyl or hexadecyl and where the cis/trans ratio is 1:1; -   dodemorph, 4-cyclododecyl-2,6-dimethylmorpholine (DE 1198125); -   fenpropimorph,     (RS)-cis-4-[3-(4-tert-butylphenyl)-2-methylpropyl]-2,6-dimethylmorpholine     (DE 27 52 096); -   tridemorph, 2,6-dimethyl-4-tridecylmorpholine (DE 11 64 152); -   fenpropidin,     (RS)-1-[3-(4-tert-butylphenyl)-2-methylpropyl]piperidine (DE 27 52     096); -   iprodione,     N-isopropyl-3-(3,5-dichlorophenyl)-2,4-dioxoimidazolidine-1-carboxamide     (GB 13 12 536); -   procymidone,     N-(3,5-dichlorophenyl)-1,2-dimethylcyclopropane-1,2-dicarboximide     (U.S. Pat. No. 3,903,090); -   vinclozolin,     3-(3,5-dichlorophenyl)-5-methyl-5-vinyloxazolidine-2,4-dione (DE-OS     22 07 576); -   famoxadone,     (RS)-3-anilino-5-methyl-5-(4-phenoxyphenyl)-1,3-oxazolidine-2,4-dione; -   fenamidone,     (S)-1-anilino-4-methyl-2-methylthio-4-phenylimidazolin-5-one; -   octhilinone, -   probenazole, 3-allyloxy-1,2-benzothiazole 1,1-dioxide; -   amisulbrom,     N,N-dimethyl-3-(3-bromo-6-fluoro-2-methylindole-1-sulfonyl)-[1,2,4]triazole-1-sulfonamide     (WO 03/053145); -   anilazine, 4,6-dichloro-N-(2-chlorophenyl)-1,3,5-triazine-2-amine     (U.S. Pat. No. 2,720,480); -   diclomezine, 6-(3,5-dichlorophenyl)-p-tolyl)pyridazin-3(2H)-one; -   pyroquilon, -   proquinazid, 6-iodo-2-propoxy-3-propylquinazolin-4(3H)-one (WO     97/48684); -   tricyclazole, 5-methyl-1,2,4-triazolo[3,4-b]benzothiazole (GB 14 19     121); -   acibenzolar-S-methyl, methyl     benzo[1,2,3]thiadiazole-7-carbothionate; -   captafol,     N-(1,1,2,2-tetrachloroethylthio)cyclohex-4-ene-1,2-dicarboximide; -   captan,     2-trichloromethylsulfanyl-3a,4,7,7a-tetrahydroisoindole-1,3-dione     (U.S. Pat. No. 2,553,770); -   dazomet, 3,5-dimethyl-1,3,5-thiadiazinane-2-thione; -   folpet, 2-trichloromethylsulfanylisoindole-1,3-dione (U.S. Pat. No.     2,553,770); -   fenoxanil,     N-(1-cyano-1,2-dimethylpropyl)-2-(2,4-dichlorophenoxy)propanamide; -   quinoxyfen, 5,7-dichloro-4-(4-fluorophenoxy)quinoline (U.S. Pat. No.     5,240,940); -   mancozeb, manganese ethylenebis(dithiocarbanate) zinc complex (U.S.     Pat. No. 3,379,610); -   maneb, manganese ethylenebis(dithiocarbamate) (U.S. Pat. No.     2,504,404); -   metam, methyldithiocarbaminic acid (U.S. Pat. No. 2,791,605); -   metiram, zinc ammoniate ethylenebis(dithiocarbamate) (U.S. Pat. No.     3,248,400); -   propineb, zinc propylenebis(dithiocarbamate) polymer (BE 611 960); -   ferbam, iron(3+) dimethyldithiocarbamate (U.S. Pat. No. 1,972,961); -   thiram, bis(dimethylthiocarbamoyl)disulfide (DE 642 532); -   ziram, dimethyldithiocarbamate; -   zineb, zinc ethylenebis(dithiocarbamate) (U.S. Pat. No. 2,457,674); -   diethofencarb, isopropyl 3,4-diethoxycarbanilate; -   iprovalicarb, isopropyl     [(1S)-2-methyl-1-(1-p-tolylethylcarbamoyl)propyl]carbamate (EP-A 472     996); -   flubenthiavalicarb (benthiavalicarb), isopropyl     {(S)-1-[(1R)-1-(6-fluorobenzothiazol-2-yl)-ethylcarbamoyl]-2-methylpropyl}carbamate     (JP-A 09/323,984); -   propamocarb, propyl 3-(dimethylamino)propylcarbamate (DE 16 43 040); -   dodine, (2,4-dichlorophenoxy)acetic acid (U.S. Pat. No. 2,867,562); -   iminoctadine, bis(8-guanidinooctyl)amine (GB 11 14 155); -   guazatine, mixture of products from the amidation of     iminodi(octamethylene)diamine, mainly iminoctadine; -   kasugamycin, 1L-1,3,4/2,5,6-1-deoxy-2,3,4,5,6-pentahydroxycyclohexyl     2-amino-2,3,4,6-tetradeoxy-4-(α-iminoglycino)-α-D-arabino-hexopyranoside; -   streptomycin,     O-2-deoxy-2-methylamino-α-L-glucopyranosyl-(1→2)-O-5-deoxy-3-C-formyl-α-L-lyxofuranosyl-(1→4)N¹,N³-diamidino-D-streptamine; -   polyoxins,     5-(2-amino-5-O-carbamoyl-2-deoxy-L-xylonamido)-1-(5-carboxy-1,2,3,4-tetrahydro-2,4-dioxopyrimidin-1-yl)-1,5-dideoxy-β-D-allofuranuronic     acid and the salts thereof; -   validamycin A, -   binapacryl, (RS)-2-sec-butyl-4,6-dinitrophenyl 3-methylcrotonate; -   dinocap, the mixture of 2,6-dinitro-4-octylphenyl crotonate and     2,4-dinitro-6-octylphenyl crotonate, wherein “octyl” is a mixture of     1-methylheptyl, 1-ethylhexyl and 1-propylpentyl (U.S. Pat. No.     2,526,660); -   dinobuton, (RS)-2-sec-butyl-4,6-dinitrophenyl isopropyl carbonate; -   dithianon,     5,10-dioxo-5,10-dihydronaphtho[2,3-b][1,4]dithiin-2,3-dicarbonitrile     (GB 857 383); -   isoprothiolane, indol-3-ylacetic acid; -   fentin acetate, triphenyltin acetate (U.S. Pat. No. 3,499,086); -   edifenphos, O-ethyl S,S-diphenyl phosphorodithioate; -   iprobenfos, S-benzyl O,O-diisopropyl phosphorothioate (Jpn.     Pesticide Inf., No. 2, S. 11 (1970)); -   fosetyl, fosetyl-aluminum, (aluminum) ethylphosphonate (FR 22 54     276); -   pyrazophos, ethyl     2-diethoxyphosphinothioyloxy-5-methylpyrazolo[1,5-a]pyrimidine-6-carboxylate     (DE 15 45 790); -   tolclofos-methyl, 0-2,6-dichloro-p-tolyl O,O-dimethyl     phosphorothioate (GB 14 67 561); -   chlorothalonil, 2,4,5,6-tetrachloroisophthalonitrile (U.S. Pat. No.     3,290,353); -   dichlofluanid,     N-dichlorofluoromethylthio-N′,N′-dimethyl-N-phenylsulfamide (DE 11     93 498); -   flusulfamide,     2′,4-dichloro-α,α,α-trifluoro-4′-nitro-m-toluenesulfanilide (EP-A     199 433); -   hexachlorobenzene (C. R. Seances Acad. Agric. Fr., Vol. 31, p. 24     (1945)); -   phthalide (DE 16 43 347); -   pencycuron, 1-(4-chlorobenzyl)-1-cyclopentyl-3-phenylurea (DE 27 32     257); -   quintozene, pentachloronitrobenzene (DE 682 048); -   thiophanate-methyl,     1,2-phenylenebis(iminocarbonothioyl)bis(dimethylcarbamate) (DE-OS 19     30 540); -   tolylfluanid,     N-dichlorofluoromethylthio-N′,N′-dimethyl-N-p-tolylsulfamide (DE 11     93 498); -   Bordeaux mixture, mixture of calcium hydroxide and copper(II)     sulfate; -   copper hydroxide, Cu(OH)₂; copper oxychloride, Cu₂Cl(OH)₃; -   cyflufenamid,     (Z)-N-[α-(cyclopropylmethoxyimino)-2,3-difluoro-6-(trifluoromethyl)benzyl]-2-phenylacetamide     (WO 96/19442); -   cymoxanil, 1-(2-cyano-2-methoxyiminoacetyl)-3-ethylurea (U.S. Pat.     No. 3,957,847); -   dimethirimol, 5-butyl-2-dimethylamino-6-methylpyrimidin-4-ol (GB 11     82 584); -   ethirimol, 5-butyl-2-ethylamino-6-methylpyrimidin-4-ol (GB 11 82     584); -   furalaxyl, methyl N-(2-furoyl)-N-(2,6-xylyl)-DL-alaninate (GB 14 48     810); -   metrafenone,     3′-bromo-2,3,4,6′-tetramethoxy-2′,6-dimethylbenzophenone (U.S. Pat.     No. 5,945,567); -   spiroxamine, (8-tert-butyl-1,4-dioxaspiro[4.5]dec-2-yl)diethylamine     (EP-A 281 842).

The compounds named according to IUPAC, their preparation and their fungicidal action are likewise known:

-   methyl     (2-chloro-5-[1-(3-methylbenzyloxyimino)ethyl]benzyl)carbamate,     methyl     (2-chloro-5-[1-(6-methylpyridin-2-ylmethoxyimino)ethyl]benzyl)carbamate     (EP-A 12 01 648); -   methyl     2-(ortho-((2,5-dimethylphenyloxymethylene)phenyl)-3-methoxyacrylate     (EP-A 226 917); -   5-chloro-7-(4-methylpiperidin-1-yl)-6-(2,4,6-trifluorophenyl)-[1,2,4]triazolo[1,5-a]pyrimidine     (WO 98/46608), -   3,4-dichloro-N-(2-cyanophenyl)isothiazole-5-carboxamide (WO     99/24413), -   N-(2-{4-[3-(4-chlorophenyl)prop-2-ynyloxy]-3-methoxyphenyl}ethyl)-2-methanesulfonylamino-3-methylbutyramide,     N-(2-{4-[3-(4-chlorophenyl)prop-2-ynyloxy]-3-methoxyphenyl}ethyl)-2-ethanesulfonylamino-3-methylbutyramide     (WO 04/049804), -   N-(4′-bromobiphenyl-2-yl)-4-difluoromethyl-2-methylthiazole-5-carboxamide,     N-(4′-trifluoromethylbiphenyl-2-yl)-4-difluoromethyl-2-methylthiazole-5-carboxamide,     N-(4′-chloro-3′-fluorobiphenyl-2-yl)-4-difluoromethyl-2-methylthiazole-5-carboxamide,     N-(3′,4′-dichloro-4-fluorobiphenyl-2-yl)-3-difluoromethyl-1-methylpyrazole-4-carboxamide     (WO 03/066609),     N-(3′,4′-dichloro-5-fluorobiphenyl-2-yl)-3-difluoromethyl-1-methylpyrazole-4-carboxamide     (WO 03/053145); -   2-butoxy-6-iodo-3-propylchromen-4-one (WO 03/14103), -   3-[5-(4-chlorophenyl)-2,3-dimethylisoxazolidin-3-yl]pyridine (EP-A     10 35 122); -   amisulbrom,     N,N-dimethyl-3-(3-bromo-6-fluoro-2-methylindole-1-sulfonyl)-[1,2,4]triazole-1-sulfonamide     (WO 03/053145), -   methyl     3-(4-chlorophenyl)-3-(2-isopropoxycarbonylamino-3-methylbutyrylamino)propanoate     (EP-A 1028125).

It is an object of the present invention, with a view to reducing the application rates and broadening the activity spectrum of the known compounds, to provide mixtures which, at a reduced total amount of active compounds applied, have improved activity against harmful fungi, in particular for certain indications.

We have found that this object is achieved by the mixtures defined at the outset. Moreover, we have found that simultaneous, that is joint or separate, application of the compounds I and an active compound II or successive application of the compounds I and an active compound II allows better control of harmful fungi than is possible with the individual compounds (synergistic mixtures). The compounds I can be used as a synergist for a large number of different active compounds. The simultaneous, that is joint or separate, application of the compound I with an active compound II increases the fungicidal activity in a superadditive manner.

The mixtures of the compounds I and an active compound II or the simultaneous, that is joint or separate, use of the compounds I and an active compound II are/is distinguished by excellent activity against a broad spectrum of phytopathogenic fungi, in particular from the classes of the Ascomycetes, Deuteromycetes, Oomycetes and Basidiomycetes. Some of them are systemically active and can be used in crop protection as foliar fungicides, as fungicides for seed dressing and as soil fungicides.

They are particularly important in the control of a multitude of fungi on various crop plants, such as bananas, cotton, vegetables (for example cucumbers, beans and cucurbits), barley, grass, oats, coffee, potatoes, corn, fruit, rice, rye, soybeans, tomatoes, grape vines, wheat, ornamental plants, sugar cane and a multiplicity of seeds.

Advantageously, they are suitable for controlling the following plant diseases:

-   -   Alternaria species on vegetables, oilseed rape, sugar beet and         fruit and rice, such as, for example, A. solani or A. alternata         on potatoes and tomatoes;     -   Aphanomyces species on sugar beet and vegetables;     -   Ascochyta species on cereals and vegetables;     -   Bipolaris and Drechslera species on corn, cereals, rice and         lawns, such as, for example, D. maydis on corn;     -   Blumeria graminis (powdery mildew) on cereals;     -   Botrytis cinerea (gray mold) on strawberries, vegetables,         flowers and grapevines;     -   Bremia lactucae on lettuce;     -   Cercospora species on corn, soybeans, rice and sugar beet;     -   Cochliobolus species on corn, cereals, rice, such as, for         example, Cochliobolus sativus on cereals, Cochliobolus         miyabeanus on rice;     -   Colletotricum species on soybeans and cotton;     -   Drechslera species, Pyrenophora species on corn, cereals, rice         and lawns, such as, for example, D. teres on barley or D.         tritici-repentis on wheat;     -   Esca on grapevines, caused by Phaeoacremonium chlamydosporium,         Ph. Aleophilum and Formitipora punctata (syn. Phellinus         punctatus);     -   Exserohilum species on corn;     -   Erysiphe cichoracearum and Sphaerotheca fuliginea on cucumbers;     -   Fusarium and Verticillium species on various plants, such as,         for example, F. graminearum or F. culmorum on cereals or F.         oxysporum on a multitude of plants, such as, for example,         tomatoes;     -   Gaeumanomyces graminis on cereals;     -   Gibberella species on cereals and rice (for example Gibberella         fujikuroi on rice);     -   Grainstaining complex on rice;     -   Helminthosporium species on corn and rice;     -   Michrodochium nivale on cereals;     -   Mycosphaerella species on cereals, bananas and groundnuts, such         as, for example, M. graminicola on wheat or M. fijiensis on         bananas;     -   Peronospora species on cabbage and bulbous plants, such as, for         example, P. brassicae on cabbage or P. destructor on onions;     -   Phakopsara pachyrhizi and Phakopsara meibomiae on soybeans;     -   Phomopsis species on soybeans and sunflowers;     -   Phytophthora infestans on potatoes and tomatoes;     -   Phytophthora species on various plants, such as, for example, P.         capsici on bell pepper;     -   Plasmopara viticola on grapevines;     -   Podosphaera leucotricha on apples;     -   Pseudocercosporella herpotrichoides on cereals;     -   Pseudoperonospora on various plants, such as, for example, P.         cubensis on cucumber or P. humili on hops;     -   Puccinia species on various plants, such as, for example, P.         triticina, P. striformins, P. hordei or P. graminis on cereals         or P. asparagi on asparagus;     -   Pyricularia oryzae, Corticium sasakii, Sarocladium oryzae, S.         attenuatum, Entyloma oryzae on rice;     -   Pyricularia grisea on lawns and cereals;     -   Pythium spp. on lawns, rice, corn, cotton, oilseed rape,         sunflowers, sugar beet, vegetables and other plants, such as,         for example, P. ultiumum on various plants, P. aphanidermatum on         lawns;     -   Rhizoctonia species on cotton, rice, potatoes, lawns, corn,         oilseed rape, potatoes, sugar beet, vegetables and on various         plants, such as, for example, R. solani on beet and various         plants;     -   Rhynchosporium secalis on barley, rye and triticale;     -   Sclerotinia species on oilseed rape and sunflowers;     -   Septoria tritici and Stagonospora nodorum on wheat;     -   Erysiphe (syn. Uncinula) necator on grapevines;     -   Setospaeria species on corn and lawns;     -   Sphacelotheca reilinia on corn;     -   Thievaliopsis species on soybeans and cotton;     -   Tilletia species on cereals;     -   Ustilago species on cereals, corn and sugar cane, such as, for         example, U. maydis on corn;     -   Venturia species (scab) on apples and pears, such as, for         example, V. inaequalis on apples.

The mixtures of the compounds I and active compounds II are suitable in particular for controlling harmful fungi from the class of the Peronosporomycetes (syn. Oomycetes), such as Peronospora species, Phytophthora species, Plasmopara viticola and Pseudoperonospora species, in particular fungi corresponding to those mentioned above.

The compounds I and active compounds II can be applied simultaneously, that is jointly or separately, or in succession, the sequence, in the case of separate application, generally not having any effect on the result of the control measures.

In the definitions of the symbols given for the formulae above, collective terms were used which generally represent the following substituents:

halogen: fluorine, chlorine, bromine and iodine; alkyl: saturated straight-chain or branched hydrocarbon radicals having 1 to 4, 6, 8 or 10 carbon atoms, for example C₁-C₆-alkyl, such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl and 1-ethyl-2-methylpropyl;

haloalkyl: straight-chain or branched alkyl groups having 1 to 2, 4 or 6 carbon atoms (as mentioned above), where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above: in particular C₁-C₂-haloalkyl, such as chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl or 1,1,1-trifluoroprop-2-yl.

With a view to the intended use of the azolopyrimidinylamines of the formula I, particular preference is given to the following meanings of the substituents, in each case on their own or in combination:

Particularly suitable for the mixtures according to the invention are compounds of the formula I in which R¹ is straight-chain or branched C₃-C₁₂-alkyl or phenyl which may be substituted by one to three halogen or C₁-C₄-alkyl groups.

In one embodiment of the compounds of the formula I, group R^(a) is absent.

A preferred embodiment relates to compounds of the formula I in which R¹ is straight-chain or branched C₅-C₁₀-alkyl, in particular ethyl, 3,5,5-trimethylhexyl, n-heptyl, n-octyl, n-nonyl and n-decyl.

A further embodiment relates to the compounds of the formula I in which R¹ is phenyl which is unsubstituted or substituted by one to four halogen, cyano, hydroxyl, mercapto, nitro, NR^(A)R^(B), C₁-C₁₀-alkyl, C₁-C₆-haloalkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl and C₁-C₆-alkoxy groups.

Preferred compounds of the formula I are those in which R¹ is a substituted phenyl group which corresponds to a group G

in which

-   L¹ is cyano, halogen, hydroxyl, mercapto, nitro, NR^(A)R^(B),     C₁-C₁₀-alkyl, C₁-C₆-haloalkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl and     C₁-C₆-alkoxy; and -   L², L³ independently of one another are hydrogen or one of the     groups mentioned under L¹ and # denotes the bond to the     azolopyrimidine skeleton.

In a further embodiment of the compounds of the formula I, L¹ is cyano, halogen, hydroxyl, mercapto, nitro, NR^(A)R^(B), C₁-C₆-alkyl, halomethyl or C₁-C₂-alkoxy, preferably cyano, halogen, C₁-C₆-alkyl, halomethyl or C₁-C₂-alkoxy.

In a further embodiment of the compounds of the formula I, L² is hydrogen or one of the groups mentioned above.

In a further embodiment of the compounds of the formula I, L³ is hydrogen, cyano, halogen, hydroxyl, mercapto, nitro, NR^(A)R^(B), C₁-C₆-alkyl, halomethyl or C₁-C₂-alkoxy, preferably hydrogen.

Preference is given to compounds of the formula I in which R² is straight-chain or branched C₁-C₁₂-alkyl, C₁-C₄-alkoxy-C₁-C₄-alkyl or C₁-C₄-haloalkyl.

In a particularly preferred embodiment of the compounds of the formula I, R² is methyl, ethyl, n-propyl, n-octyl, trifluoromethyl or methoxymethyl, in particular methyl, ethyl, trifluoromethyl or methoxymethyl.

Preference is furthermore given to compounds of the formula I in which R³ is hydrogen.

In a further embodiment of the compounds of the formula I, R³ is amino.

One embodiment of the compounds of the formula I relates to those in which A is N. These compounds correspond to the formula IA in which the variables are as defined for formula I:

Another embodiment of the compounds of the formula I relates to those in which A is CH. These compounds correspond to the formula IB in which the variables are as defined for formula I:

In a further embodiment of preferred compounds I, the carbon chains of R¹ and R² together do not have more than 12 carbon atoms.

Especially preferred with a view to their use are the compounds I compiled in the tables below. The groups mentioned for a substituent in the tables are furthermore per se, independently of the combination in which they are mentioned, a particularly preferred embodiment of the substituent in question.

Table 1

Compounds of the formula IA in which the combination of R¹, R² and R³ for a compound corresponds in each case to one row of Table I

Table 2

Compounds of the formula IB in which the combination of R¹, R² and R³ for a compound corresponds in each case to one row of Table I

TABLE I No. R¹ R² R³ I-1 C₆H₅ CH₃ H I-2 2-Cl—C₆H₄ CH₃ H I-3 3-Cl—C₆H₄ CH₃ H I-4 4-Cl—C₆H₄ CH₃ H I-5 2-F—C₆H₄ CH₃ H I-6 3-F—C₆H₄ CH₃ H I-7 4-F—C₆H₄ CH₃ H I-8 2,4-Cl₂—C₆H₃ CH₃ H I-9 3,4-Cl₂—C₆H₃ CH₃ H I-10 2,4-F₂—C₆H₃ CH₃ H I-11 3,4-F₂—C₆H₃ CH₃ H I-12 4-CH₃—C₆H₄ CH₃ H I-13 4-CH₂CH₃—C₆H₄ CH₃ H I-14 4-CH₂CH₂CH₃—C₆H₄ CH₃ H I-15 4-CH(CH₃)₂—C₆H₄ CH₃ H I-16 4-CH₂CH₂CH₂CH₃—C₆H₄ CH₃ H I-17 4-C(CH₃)CH₂CH₃—C₆H₄ CH₃ H I-18 4-C(CH₃)₃—C₆H₄ CH₃ H I-19 CH₂CH₂CH₂CH₃ CH₃ H I-20 CH₂CH₂CH₂CH₂CH₃ CH₃ H I-21 CH₂CH₂CH₂CH₂CH₂CH₃ CH₃ H I-22 CH₂CH(CH₃)CH₂CH₂CH₃ CH₃ H I-23 CH₂CH(CH₂CH₃)₂ CH₃ H I-24 CH₂CH₂CH₂CH₂CH₂CH₂CH₃ CH₃ H I-25 CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₃ CH₃ H I-26 CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₃ CH₃ H I-27 CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₃ CH₃ H I-28 CH₂CH₂CH(CH₃)CH₂CH(CH₃)₃ CH₃ H I-29 CH₂CH₂CH₂CH₃ CH₃ NH₂ I-30 CH₂CH₂CH₂CH₂CH₃ CH₃ NH₂ I-31 CH₂CH₂CH₂CH₂CH₂CH₃ CH₃ NH₂ I-32 CH₂CH(CH₃)CH₂CH₂CH₃ CH₃ NH₂ I-33 CH₂CH(CH₂CH₃)₂ CH₃ NH₂ I-34 CH₂CH₂CH₂CH₂CH₂CH₂CH₃ CH₃ NH₂ I-35 CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₃ CH₃ NH₂ I-64 (CH₂)₃—O—CH₂CH(CH₂CH₃)CH₂CH₂CH₃ CH₃ H I-65 (CH₂)₃—O—CH₂CH₂CH(CH₃)CH₂CH(CH₃)₂ CH₃ H I-66 (CH₂)₃—O—CH₂CH₂CH(CH₃)CH₂C(CH₃)₃ CH₃ H I-67 (CH₂)₃—O—CH₂CH₂CH(CH₃)CH₂CH₂CH(CH₃)₂ CH₃ H I-68 (CH₂)₃—O—CH₂CH₂CH(CH₃)CH₂CH₂CH₂CH(CH₃)₂ CH₃ H I-69 (CH₂)₃—O—CH₃ CH₃ CH₃ I-70 (CH₂)₃—O—CH₂CH₃ CH₃ CH₃ I-71 (CH₂)₃—O—CH₂CH₂CH₃ CH₃ CH₃ I-72 (CH₂)₃—O—CH₂CH₂CH₂CH₃ CH₃ CH₃ I-73 (CH₂)₃—O—CH₂CH₂CH₂CH₂CH₃ CH₃ CH₃ I-74 (CH₂)₃—O—CH₂CH₂CH₂CH₂CH₂CH₃ CH₃ CH₃ I-75 (CH₂)₃—O—CH₂CH₂CH₂CH₂CH₂CH₂CH₃ CH₃ CH₃ I-76 (CH₂)₃—O—CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₃ CH₃ CH₃ I-77 (CH₂)₃—O—CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₃ CH₃ CH₃ I-78 (CH₂)₃—O—CH(CH₃)₂ CH₃ CH₃ I-79 (CH₂)₃—O—C(CH₃)₃ CH₃ CH₃ I-80 (CH₂)₃—O—CH₂C(CH₃)₃ CH₃ CH₃ I-81 (CH₂)₃—O—CH(CH₃)CH₂C(CH₃)₃ CH₃ CH₃ I-82 (CH₂)₃—O—CH(CH₂CH₃)CH₂C(CH₃)₃ CH₃ CH₃ I-83 (CH₂)₃—O—CH₂CH(CH₃)CH₂CH(CH₃)₂ CH₃ CH₃ I-84 (CH₂)₃—O—CH₂CH(CH₂CH₃)CH₂CH₂CH₃ CH₃ CH₃ I-85 (CH₂)₃—O—CH₂CH₂CH(CH₃)CH₂CH(CH₃)₂ CH₃ CH₃ I-86 (CH₂)₃—O—CH₂CH₂CH(CH₃)CH₂C(CH₃)₃ CH₃ CH₃ I-87 (CH₂)₃—O—CH₂CH₂CH(CH₃)CH₂CH₂CH(CH₃)₂ CH₃ CH₃ I-88 (CH₂)₃—O—CH₂CH₂CH(CH₃)CH₂CH₂CH₂CH(CH₃)₂ CH₃ CH₃ I-89 CH₂—C₆H₅ CF₃ H I-90 CH₂-(4-Cl—C₆H₄) CF₃ H I-91 CH₂CH₂CH₃ CF₃ H I-92 CH₂CH₂CH₂CH₃ CF₃ H I-93 CH₂CH₂CH₂CH₂CH₃ CF₃ H I-94 CH₂CH₂CH₂CH₂CH₂CH₃ CF₃ H I-95 CH₂CH(CH₃)CH₂CH₂CH₃ CF₃ H I-96 CH₂CH(CH₂CH₃)₂ CF₃ H I-97 CH₂CH₂CH₂CH₂CH₂CH₂CH₃ CF₃ H I-98 CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₃ CF₃ H I-99 CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₃ CF₃ H I-100 CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₃ CF₃ H I-101 CH₂CH₂CH(CH₃)CH₂CH(CH₃)₃ CF₃ H I-102 cyclo-C₅H₉ CF₃ H I-103 cyclo-C₆H₁₁ CF₃ H I-104 CH₂CH₂CH₂CH₃ CH₂CH₃ H I-105 CH₂CH₂CH₂CH₂CH₃ CH₂CH₃ H I-106 CH₂CH₂CH₂CH₂CH₂CH₃ CH₂CH₃ H I-107 CH₂CH(CH₃)CH₂CH₂CH₃ CH₂CH₃ H I-108 CH₂CH(CH₂CH₃)₂ CH₂CH₃ H I-109 CH₂CH₂CH₂CH₂CH₂CH₂CH₃ CH₂CH₃ H I-110 CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₃ CH₂CH₃ H I-111 CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₃ CH₂CH₃ H I-112 CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₃ CH₂CH₃ H I-113 CH₂CH₂CH(CH₃)CH₂CH(CH₃)₃ CH₂CH₃ H I-114 CH₂CH₂CH₂CH₃ CH₂CH₃ NH₂ I-115 CH₂CH₂CH₂CH₂CH₃ CH₂CH₃ NH₂ I-116 CH₂CH₂CH₂CH₂CH₂CH₃ CH₂CH₃ NH₂ I-117 CH₂CH(CH₃)CH₂CH₂CH₃ CH₂CH₃ NH₂ I-118 CH₂CH(CH₂CH₃)₂ CH₂CH₃ NH₂ I-119 CH₂CH₂CH₂CH₂CH₂CH₂CH₃ CH₂CH₃ NH₂ 1-120 CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₃ CH₂CH₃ NH₂ I-121 CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₃ CH₂CH₃ NH₂ I-122 CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₃ CH₂CH₃ NH₂ I-123 CH₂CH₂CH(CH₃)CH₂CH(CH₃)₃ CH₂CH₃ NH₂ I-124 CH₂CH₂CH₂CH₃ CH₂CH₃ CH₃ I-125 CH₂CH₂CH₂CH₂CH₃ CH₂CH₃ CH₃ I-126 CH₂CH₂CH₂CH₂CH₂CH₃ CH₂CH₃ CH₃ I-127 CH₂CH(CH₃)CH₂CH₂CH₃ CH₂CH₃ CH₃ I-128 CH₂CH(CH₂CH₃)₂ CH₂CH₃ CH₃ I-129 CH₂CH₂CH₂CH₂CH₂CH₂CH₃ CH₂CH₃ CH₃ I-130 CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₃ CH₂CH₃ CH₃ I-131 CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₃ CH₂CH₃ CH₃ I-132 CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₃ CH₂CH₃ CH₃ I-133 CH₂CH₂CH(CH₃)CH₂CH(CH₃)₃ CH₂CH₃ CH₃ I-134 (CH₂)₃—O—CH₃ CH₂CH₃ H I-135 (CH₂)₃—O—CH₂CH₃ CH₂CH₃ H I-136 (CH₂)₃—O—CH₂CH₂CH₃ CH₂CH₃ H I-137 (CH₂)₃—O—CH₂CH₂CH₂CH₃ CH₂CH₃ H I-138 (CH₂)₃—O—CH₂CH₂CH₂CH₂CH₃ CH₂CH₃ H I-139 (CH₂)₃—O—CH₂CH₂CH₂CH₂CH₂CH₃ CH₂CH₃ H I-140 (CH₂)₃—O—CH₂CH₂CH₂CH₂CH₂CH₂CH₃ CH₂CH₃ H I-141 (CH₂)₃—O—CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₃ CH₂CH₃ H I-142 (CH₂)₃—O—CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₃ CH₂CH₃ H I-143 (CH₂)₃—O—CH(CH₃)₂ CH₂CH₃ H I-144 (CH₂)₃—O—C(CH₃)₃ CH₂CH₃ H I-145 (CH₂)₃—O—CH₂C(CH₃)₃ CH₂CH₃ H I-146 (CH₂)₃—O—CH(CH₃)CH₂C(CH₃)₃ CH₂CH₃ H I-147 (CH₂)₃—O—CH(CH₂CH₃)CH₂C(CH₃)₃ CH₂CH₃ H I-148 (CH₂)₃—O—CH₂CH(CH₃)CH₂CH(CH₃)₂ CH₂CH₃ H I-149 (CH₂)₃—O—CH₂CH(CH₂CH₃)CH₂CH₂CH₃ CH₂CH₃ H I-150 (CH₂)₃—O—CH₂CH₂CH(CH₃)CH₂CH(CH₃)₂ CH₂CH₃ H I-151 (CH₂)₃—O—CH₂CH₂CH(CH₃)CH₂C(CH₃)₃ CH₂CH₃ H I-152 (CH₂)₃—O—CH₂CH₂CH(CH₃)CH₂CH₂CH(CH₃)₂ CH₂CH₃ H I-153 (CH₂)₃—O—CH₂CH₂CH(CH₃)CH₂CH₂CH₂CH(CH₃)₂ CH₂CH₃ H I-154 (CH₂)₃—O—CH₃ CH₂CH₃ CH₃ I-155 (CH₂)₃—O—CH₂CH₃ CH₂CH₃ CH₃ I-156 (CH₂)₃—O—CH₂CH₂CH₃ CH₂CH₃ CH₃ I-157 (CH₂)₃—O—CH₂CH₂CH₂CH₃ CH₂CH₃ CH₃ I-158 (CH₂)₃—O—CH₂CH₂CH₂CH₂CH₃ CH₂CH₃ CH₃ I-159 (CH₂)₃—O—CH₂CH₂CH₂CH₂CH₂CH₃ CH₂CH₃ CH₃ I-160 (CH₂)₃—O—CH₂CH₂CH₂CH₂CH₂CH₂CH₃ CH₂CH₃ CH₃ I-161 (CH₂)₃—O—CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₃ CH₂CH₃ CH₃ I-162 (CH₂)₃—O—CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₃ CH₂CH₃ CH₃ I-163 (CH₂)₃—O—CH(CH₃)₂ CH₂CH₃ CH₃ I-164 (CH₂)₃—O—C(CH₃)₃ CH₂CH₃ CH₃ I-165 (CH₂)₃—O—CH₂C(CH₃)₃ CH₂CH₃ CH₃ I-166 (CH₂)₃—O—CH(CH₃)CH₂C(CH₃)₃ CH₂CH₃ CH₃ I-167 (CH₂)₃—O—CH(CH₂CH₃)CH₂C(CH₃)₃ CH₂CH₃ CH₃ I-168 (CH₂)₃—O—CH₂CH(CH₃)CH₂CH(CH₃)₂ CH₂CH₃ CH₃ I-169 (CH₂)₃—O—CH₂CH(CH₂CH₃)CH₂CH₂CH₃ CH₂CH₃ CH₃ I-170 (CH₂)₃—O—CH₂CH₂CH(CH₃)CH₂CH(CH₃)₂ CH₂CH₃ CH₃ I-171 (CH₂)₃—O—CH₂CH₂CH(CH₃)CH₂C(CH₃)₃ CH₂CH₃ CH₃ I-172 (CH₂)₃—O—CH₂CH₂CH(CH₃)CH₂CH₂CH(CH₃)₂ CH₂CH₃ CH₃ I-173 (CH₂)₃—O—CH₂CH₂CH(CH₃)CH₂CH₂CH₂CH(CH₃)₂ CH₂CH₃ CH₃ I-174 CH₂CH₂CH₂CH₃ CH₂CH₂CH₃ H I-175 CH₂CH₂CH₂CH₂CH₃ CH₂CH₂CH₃ H I-176 CH₂CH₂CH₂CH₂CH₂CH₃ CH₂CH₂CH₃ H I-177 CH₂CH(CH₃)CH₂CH₂CH₃ CH₂CH₂CH₃ H I-178 CH₂CH(CH₂CH₃)₂ CH₂CH₂CH₃ H I-179 CH₂CH₂CH₂CH₂CH₂CH₂CH₃ CH₂CH₂CH₃ H I-180 CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₃ CH₂CH₂CH₃ H I-181 CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₃ CH₂CH₂CH₃ H I-182 CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₃ CH₂CH₂CH₃ H I-183 CH₂CH₂CH(CH₃)CH₂CH(CH₃)₃ CH₂CH₂CH₃ H I-184 CH₂—O—CH₂CH₂CH₂CH₃ CH₂CH₂CH₃ H I-185 CH₂—O—CH₂CH₂CH₂CH₂CH₃ CH₂CH₂CH₃ H I-186 CH₂—O—CH₂CH₂CH₂CH₂CH₂CH₃ CH₂CH₂CH₃ H I-187 CH₂—O—CH₂CH₂CH₂CH₂CH₂CH₂CH₃ CH₂CH₂CH₃ H I-188 CH₂—O—CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₃ CH₂CH₂CH₃ H I-189 CH₂—O—CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₃ CH₂CH₂CH₃ H I-190 CH₂—O—C(CH₃)₃ CH₂CH₂CH₃ H I-191 CH₂—O—CH₂C(CH₃)₃ CH₂CH₂CH₃ H I-192 CH₂—O—CH(CH₃)CH₂C(CH₃)₃ CH₂CH₂CH₃ H I-193 CH₂—O—CH(CH₂CH₃)CH₂C(CH₃)₃ CH₂CH₂CH₃ H I-194 CH₂—O—CH₂CH(CH₃)CH₂CH(CH₃)₂ CH₂CH₂CH₃ H I-195 CH₂—O—CH₂CH(CH₂CH₃)CH₂CH₂CH₃ CH₂CH₂CH₃ H I-196 CH₂—O—CH₂CH₂CH(CH₃)CH₂CH(CH₃)₂ CH₂CH₂CH₃ H I-197 CH₂—O—CH₂CH₂CH(CH₃)CH₂C(CH₃)₃ CH₂CH₂CH₃ H I-198 CH₂—O—CH₂CH₂CH(CH₃)CH₂CH₂CH(CH₃)₂ CH₂CH₂CH₃ H I-199 CH₂—O—CH₂CH₂CH(CH₃)CH₂CH₂CH₂CH(CH₃)₂ CH₂CH₂CH₃ H I-200 (CH₂)₂—O—CH₂CH₂CH₃ CH₂CH₂CH₃ H I-201 (CH₂)₂—O—CH₂CH₂CH₂CH₃ CH₂CH₂CH₃ H I-202 (CH₂)₂—O—CH₂CH₂CH₂CH₂CH₃ CH₂CH₂CH₃ H I-203 (CH₂)₂—O—CH₂CH₂CH₂CH₂CH₂CH₃ CH₂CH₂CH₃ H I-204 (CH₂)₂—O—CH₂CH₂CH₂CH₂CH₂CH₂CH₃ CH₂CH₂CH₃ H I-205 (CH₂)₂—O—CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₃ CH₂CH₂CH₃ H I-206 (CH₂)₂—O—CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₃ CH₂CH₂CH₃ H I-207 (CH₂)₂—O—CH(CH₃)₂ CH₂CH₂CH₃ H I-208 (CH₂)₂—O—C(CH₃)₃ CH₂CH₂CH₃ H I-209 (CH₂)₂—O—CH₂C(CH₃)₃ CH₂CH₂CH₃ H I-210 (CH₂)₂—O—CH(CH₃)CH₂C(CH₃)₃ CH₂CH₂CH₃ H I-211 (CH₂)₂—O—CH(CH₂CH₃)CH₂C(CH₃)₃ CH₂CH₂CH₃ H I-212 (CH₂)₂—O—CH₂CH(CH₃)CH₂CH(CH₃)₂ CH₂CH₂CH₃ H I-213 (CH₂)₂—O—CH₂CH(CH₂CH₃)CH₂CH₂CH₃ CH₂CH₂CH₃ H I-214 (CH₂)₂—O—CH₂CH₂CH(CH₃)CH₂CH(CH₃)₂ CH₂CH₂CH₃ H I-215 (CH₂)₂—O—CH₂CH₂CH(CH₃)CH₂C(CH₃)₃ CH₂CH₂CH₃ H I-216 (CH₂)₂—O—CH₂CH₂CH(CH₃)CH₂CH₂CH(CH₃)₂ CH₂CH₂CH₃ H I-217 (CH₂)₂—O—CH₂CH₂CH(CH₃)CH₂CH₂CH₂CH(CH₃)₂ CH₂CH₂CH₃ H I-218 (CH₂)₃—O—CH₃ CH₂CH₂CH₃ H I-219 (CH₂)₃—O—CH₂CH₃ CH₂CH₂CH₃ H I-220 (CH₂)₃—O—CH₂CH₂CH₃ CH₂CH₂CH₃ H I-221 (CH₂)₃—O—CH₂CH₂CH₂CH₃ CH₂CH₂CH₃ H I-222 (CH₂)₃—O—CH₂CH₂CH₂CH₂CH₃ CH₂CH₂CH₃ H I-223 (CH₂)₃—O—CH₂CH₂CH₂CH₂CH₂CH₃ CH₂CH₂CH₃ H I-224 (CH₂)₃—O—CH₂CH₂CH₂CH₂CH₂CH₂CH₃ CH₂CH₂CH₃ H I-225 (CH₂)₃—O—CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₃ CH₂CH₂CH₃ H I-226 (CH₂)₃—O—CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₃ CH₂CH₂CH₃ H I-227 (CH₂)₃—O—CH(CH₃)₂ CH₂CH₂CH₃ H I-228 (CH₂)₃—O—C(CH₃)₃ CH₂CH₂CH₃ H I-229 (CH₂)₃—O—CH₂C(CH₃)₃ CH₂CH₂CH₃ H I-230 (CH₂)₃—O—CH(CH₃)CH₂C(CH₃)₃ CH₂CH₂CH₃ H I-231 (CH₂)₃—O—CH(CH₂CH₃)CH₂C(CH₃)₃ CH₂CH₂CH₃ H I-232 (CH₂)₃—O—CH₂CH(CH₃)CH₂CH(CH₃)₂ CH₂CH₂CH₃ H I-233 (CH₂)₃—O—CH₂CH(CH₂CH₃)CH₂CH₂CH₃ CH₂CH₂CH₃ H I-234 (CH₂)₃—O—CH₂CH₂CH(CH₃)CH₂CH(CH₃)₂ CH₂CH₂CH₃ H I-235 (CH₂)₃—O—CH₂CH₂CH(CH₃)CH₂C(CH₃)₃ CH₂CH₂CH₃ H I-236 (CH₂)₃—O—CH₂CH₂CH(CH₃)CH₂CH₂CH(CH₃)₂ CH₂CH₂CH₃ H I-237 (CH₂)₃—O—CH₂CH₂CH(CH₃)CH₂CH₂CH₂CH(CH₃)₂ CH₂CH₂CH₃ H I-238 CH₂CH₂CH₃ CH₂OCH₃ H I-239 CH₂CH₂CH₂CH₃ CH₂OCH₃ H I-240 CH₂CH₂CH₂CH₂CH₃ CH₂OCH₃ H I-241 CH₂CH₂CH₂CH₂CH₂CH₃ CH₂OCH₃ H I-242 CH₂CH(CH₃)CH₂CH₂CH₃ CH₂OCH₃ H I-243 CH₂CH(CH₂CH₃)₂ CH₂OCH₃ H I-244 CH₂CH₂CH₂CH₂CH₂CH₂CH₃ CH₂OCH₃ H I-245 CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₃ CH₂OCH₃ H I-246 CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₃ CH₂OCH₃ H I-247 CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₃ CH₂OCH₃ H I-248 CH₂CH₂CH(CH₃)CH₂CH(CH₃)₃ CH₂OCH₃ H I-249 (CH₂)₃—O—CH₃ CH₂OCH₃ H I-250 (CH₂)₃—O—CH₂CH₃ CH₂OCH₃ H I-251 (CH₂)₃—O—CH₂CH₂CH₃ CH₂OCH₃ H I-252 (CH₂)₃—O—CH₂CH₂CH₂CH₃ CH₂OCH₃ H I-253 (CH₂)₃—O—CH₂CH₂CH₂CH₂CH₃ CH₂OCH₃ H I-254 (CH₂)₃—O—CH₂CH₂CH₂CH₂CH₂CH₃ CH₂OCH₃ H I-255 (CH₂)₃—O—CH₂CH₂CH₂CH₂CH₂CH₂CH₃ CH₂OCH₃ H I-256 (CH₂)₃—O—CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₃ CH₂OCH₃ H I-257 (CH₂)₃—O—CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₃ CH₂OCH₃ H I-258 (CH₂)₃—O—CH(CH₃)₂ CH₂OCH₃ H I-259 (CH₂)₃—O—C(CH₃)₃ CH₂OCH₃ H I-260 (CH₂)₃—O—CH₂C(CH₃)₃ CH₂OCH₃ H I-261 (CH₂)₃—O—CH(CH₃)CH₂C(CH₃)₃ CH₂OCH₃ H I-262 (CH₂)₃—O—CH(CH₂CH₃)CH₂C(CH₃)₃ CH₂OCH₃ H I-263 (CH₂)₃—O—CH₂CH(CH₃)CH₂CH(CH₃)₂ CH₂OCH₃ H I-264 (CH₂)₃—O—CH₂CH(CH₂CH₃)CH₂CH₂CH₃ CH₂OCH₃ H I-265 (CH₂)₃—O—CH₂CH₂CH(CH₃)CH₂CH(CH₃)₂ CH₂OCH₃ H I-266 (CH₂)₃—O—CH₂CH₂CH(CH₃)CH₂C(CH₃)₃ CH₂OCH₃ H I-267 (CH₂)₃—O—CH₂CH₂CH(CH₃)CH₂CH₂CH(CH₃)₂ CH₂OCH₃ H I-268 (CH₂)₃—O—CH₂CH₂CH(CH₃)CH₂CH₂CH₂CH(CH₃)₂ CH₂OCH₃ H I-269 CH₃ (CH₂)₃CH₃ H I-270 CH₂CH₃ (CH₂)₃CH₃ H I-271 CH₂CH₂CH₃ (CH₂)₃CH₃ H I-272 CH₂CH₂CH₂CH₃ (CH₂)₃CH₃ H I-273 CH₂CH₂CH₂CH₂CH₃ (CH₂)₃CH₃ H I-274 CH₃ (CH₂)₄CH₃ H I-275 CH₂CH₃ (CH₂)₄CH₃ H I-276 CH₂CH₂CH₃ (CH₂)₄CH₃ H I-277 CH₂CH₂CH₂CH₃ (CH₂)₄CH₃ H I-278 CH₂CH₂CH₂CH₂CH₃ (CH₂)₄CH₃ H I-279 CH₃ (CH₂)₅CH₃ H I-280 CH₂CH₃ (CH₂)₅CH₃ H I-281 CH₂CH₂CH₃ (CH₂)₅CH₃ H I-282 CH₂CH₂CH₂CH₃ (CH₂)₅CH₃ H I-283 CH₂CH₂CH₂CH₂CH₃ (CH₂)₅CH₃ H I-284 CH₃ (CH₂)₆CH₃ H I-285 CH₂CH₃ (CH₂)₆CH₃ H I-286 CH₂CH₂CH₃ (CH₂)₆CH₃ H I-287 CH₂CH₂CH₂CH₃ (CH₂)₆CH₃ H I-288 CH₂CH₂CH₂CH₂CH₃ (CH₂)₆CH₃ H I-289 CH₃ (CH₂)₇CH₃ H I-290 CH₂CH₃ (CH₂)₇CH₃ H I-291 CH₂CH₂CH₃ (CH₂)₇CH₃ H I-292 CH₂CH₂CH₂CH₃ (CH₂)₇CH₃ H I-293 CH₂CH₂CH₂CH₂CH₃ (CH₂)₇CH₃ H I-294 CH₃ (CH₂)₈CH₃ H I-295 CH₂CH₃ (CH₂)₈CH₃ H I-296 CH₂CH₂CH₃ (CH₂)₈CH₃ H I-297 CH₂CH₂CH₂CH₃ (CH₂)₈CH₃ H I-298 CH₂CH₂CH₂CH₂CH₃ (CH₂)₈CH₃ H

Preferred embodiments of the mixtures according to the invention comprise, as active component 1, a compound selected from the following list:

-   6-(3,4-dichlorophenyl)-5-methyl-[1,2,4]triazolo[1,5-a]pyrimidin-7-ylamine, -   6-(4-tert-butylphenyl)-5-methyl-[1,2,4]triazolo[1,5-a]pyrimidin-7-ylamine, -   5-methyl-6-(3,5,5-trimethylhexyl)-[1,2,4]triazolo[1,5-a]pyrimidin-7-ylamine, -   5-methyl-6-octyl-[1,2,4]triazolo[1,5-a]pyrimidin-7-ylamine, -   5-ethyl-6-octyl-[1,2,4]triazolo[1,5-a]pyrimidine-2,7-diamine, -   6-ethyl-5-octyl-[1,2,4]triazolo[1,5-a]pyrimidin-7-ylamine, -   5-ethyl-6-octyl-[1,2,4]triazolo[1,5-a]pyrimidin-7-ylamine, -   5-ethyl-6-(3,5,5-trimethylhexyl)-[1,2,4]triazolo[1,5-a]pyrimidin-7-ylamine, -   6-octyl-5-propyl-[1,2,4]triazolo[1,5-a]pyrimidin-7-ylamine, -   5-methoxymethyl-6-octyl-[1,2,4]triazolo[1,5-a]pyrimidin-7-ylamine, -   6-octyl-5-trifluoromethyl-[1,2,4]triazolo[1,5-a]pyrimidin-7-ylamine     and -   5-trifluoromethyl-6-(3,5,5-trimethylhexyl)-[1,2,4]triazolo[1,5-a]pyrimidin-7-ylamine.

Further preferred embodiments of the mixtures according to the invention relate to combinations of one of the compounds of Table 1, in particular one of the preferred compounds I hereinabove, and one of the following active compounds II:

-   -   A) azoles, such as cyproconazole, difenoconazole,         fluquinconazole, flusilazole, metconazole, propiconazole,         prothioconazole, tebuconazole         -   prochloraz, cyazofamid;         -   carbendazim;         -   ethaboxam;     -   B) strobilurins, such as azoxystrobin, enestroburin,         fluoxastrobin, pyraclostrobin, trifloxystrobin or methyl         (2-chloro-5-[1-(3-methylbenzyloxyimino)-ethyl]benzyl)carbamate         [B-6], methyl         (2-chloro-5-[1-(6-methylpyridin-2-ylmethoxy-imino)ethyl]benzyl)carbamate         [B-7];     -   C) carboxamides, such as benalaxyl, boscalid, metalaxyl,         ofurace, oxadixyl, dimethomorph;         -   fluopicolide (picobenzamid), zoxamide;         -   mandipropamid;     -   D) heterocylic compounds, such as fluazinam;         -   cyprodinil, pyrimethanil;         -   dodemorph,         -   iprodione, vinclozolin;         -   famoxadone, fenamidone;         -   amisulbrom;         -   5-chloro-7-(4-methylpiperidin-1-yl)-6-(2,4,6-trifluorophenyl)-[1,2,4]triazolo[1,5-a]pyrimidine             [D-8],         -   captan, folpet;     -   E) carbamates, such as mancozeb, maneb, metiram, propineb;         -   iprovalicarb, flubenthiavalicarb;         -   methyl             3-(4-chlorophenyl)-3-(2-isopropoxycarbonylamino-3-methyl-butyrylamino)propanoate             [E-7];     -   and     -   F) other active compounds, selected from         -   sulfur-containing heterocyclyl compounds: dithianon;         -   organophosphorus compounds: fosetyl, fosetyl-aluminum,             phosphorous acid and its salts;         -   organochlorine compounds: chlorothalonil,             thiophanate-methyl;         -   inorganic active compounds: Bordeaux mixture, copper             acetate, copper hydroxide, copper oxychloride, basic copper             sulfate;         -   others: cymoxanil, metrafenone;         -   growth retardants: prohexadione and its salts.

Preferred embodiments relate to the compositions listed in table A, where in each case one row of table A corresponds to a fungicidal composition comprising the particular compound of the formula I mentioned (component 1) and one active compound of the groups mentioned, this active compound preferably being selected from the preferred embodiments defined above.

TABLE A Row Component 1 Component 2 A-1 Tab. 1, I-9 an active compound II from group A A-2 Tab. 1, I-9 an active compound II from group B A-3 Tab. 1, I-9 an active compound II from group C A-4 Tab. 1, I-9 an active compound II from group D A-5 Tab. 1, I-9 an active compound II from group E A-6 Tab. 1, I-9 an active compound II from group F A-7 Tab. 1, I-18 an active compound II from group A A-8 Tab. 1, I-18 an active compound II from group B A-9 Tab. 1, I-18 an active compound II from group C A-10 Tab. 1, I-18 an active compound II from group D A-11 Tab. 1, I-18 an active compound II from group E A-12 Tab. 1, I-18 an active compound II from group F A-13 Tab. 1, I-25 an active compound II from group A A-14 Tab. 1, I-25 an active compound II from group B A-15 Tab. 1, I-25 an active compound II from group C A-16 Tab. 1, I-25 an active compound II from group D A-17 Tab. 1, I-25 an active compound II from group E A-18 Tab. 1, I-25 an active compound II from group F A-19 Tab. 1, I-28 an active compound II from group A A-20 Tab. 1, I-28 an active compound II from group B A-21 Tab. 1, I-28 an active compound II from group C A-22 Tab. 1, I-28 an active compound II from group D A-23 Tab. 1, I-28 an active compound II from group E A-24 Tab. 1, I-28 an active compound II from group F A-25 Tab. 1, I-98 an active compound II from group A A-26 Tab. 1, I-98 an active compound II from group B A-27 Tab. 1, I-98 an active compound II from group C A-28 Tab. 1, I-98 an active compound II from group D A-29 Tab. 1, I-98 an active compound II from group E A-30 Tab. 1, I-98 an active compound II from group F A-31 Tab. 1, I-101 an active compound II from group A A-32 Tab. 1, I-101 an active compound II from group B A-33 Tab. 1, I-101 an active compound II from group C A-34 Tab. 1, I-101 an active compound II from group D A-35 Tab. 1, I-101 an active compound II from group E A-36 Tab. 1, I-101 an active compound II from group F A-37 Tab. 1, I-110 an active compound II from group A A-38 Tab. 1, I-110 an active compound II from group B A-39 Tab. 1, I-110 an active compound II from group C A-40 Tab. 1, I-110 an active compound II from group D A-41 Tab. 1, I-110 an active compound II from group E A-42 Tab. 1, I-110 an active compound II from group F A-43 Tab. 1, I-113 an active compound II from group A A-44 Tab. 1, I-113 an active compound II from group B A-45 Tab. 1, I-113 an active compound II from group C A-46 Tab. 1, I-113 an active compound II from group D A-47 Tab. 1, I-113 an active compound II from group E A-48 Tab. 1, I-113 an active compound II from group F A-49 Tab. 1, I-120 an active compound II from group A A-50 Tab. 1, I-120 an active compound II from group B A-51 Tab. 1, I-120 an active compound II from group C A-52 Tab. 1, I-120 an active compound II from group D A-53 Tab. 1, I-120 an active compound II from group E A-54 Tab. 1, I-120 an active compound II from group F A-55 Tab. 1, I-180 an active compound II from group A A-56 Tab. 1, I-180 an active compound II from group B A-57 Tab. 1, I-180 an active compound II from group C A-58 Tab. 1, I-180 an active compound II from group D A-59 Tab. 1, I-180 an active compound II from group E A-60 Tab. 1, I-180 an active compound II from group F A-61 Tab. 1, I-245 an active compound II from group A A-62 Tab. 1, I-245 an active compound II from group B A-63 Tab. 1, I-245 an active compound II from group C A-64 Tab. 1, I-245 an active compound II from group D A-65 Tab. 1, I-245 an active compound II from group E A-66 Tab. 1, I-245 an active compound II from group F A-67 Tab. 1, I-290 an active compound II from group A A-68 Tab. 1, I-290 an active compound II from group B A-69 Tab. 1, I-290 an active compound II from group C A-70 Tab. 1, I-290 an active compound II from group D A-71 Tab. 1, I-290 an active compound II from group E A-72 Tab. 1, I-290 an active compound II from group F

The active compounds mentioned above can also be employed in the form of their agriculturally compatible salts. These are usually the alkali metal or alkaline earth metal salts, such as sodium, potassium or calcium salts.

When preparing the mixtures, preference is given to using the pure active compounds which, if required, may be mixed with further active compounds against harmful fungi or other pests, such as insects, arachnids or nematodes, or else herbicidal or growth-regulating active compounds or fertilizers as further active components.

In a preferred embodiment of the invention, mixtures of an azolopyrimidinylamine and an active compound II are used. Under certain conditions, it may be advantageous to combine an azolopyrimidinylamine with two or more active compounds II. In addition, mixtures of two or more compounds I with one or more active compounds II may also be suitable.

Suitable further active components in the above sense are in particular the active compounds II, mentioned at the outset, and in particular the preferred active compounds mentioned above. In the case of ternary mixtures, preferred third active components are strobilurins, in particular pyraclostrobin, carboxamides, in particular boscalid, and also organophosphorus compounds, in particular phosphorous acid and its salts.

The compounds I and active compounds II are usually employed in a weight ratio of from 100:1 to 1:100, preferably from 50:1 to 1:50, preferably from 20:1 to 1:20, in particular from 10:1 to 1:10.

The further active components are, if desired, added in a ratio of from 50:1 to 1:50, preferably from 20:1 to 1:20, to the compound I.

Depending on the type of compound and the desired effect, the application rates of the mixtures according to the invention are from 5 g/ha to 2000 g/ha, preferably from 50 to 900 g/ha, in particular from 50 to 750 g/ha.

Correspondingly, the application rates for compounds I are generally from 1 to 1000 g/ha, preferably from 10 to 900 g/ha, in particular from 20 to 750 g/ha.

Depending on the type of active compound II, the application rates for active compounds II are generally from 1 to 2000 g/ha, preferably from 10 to 900 g/ha, in particular from 40 to 500 g/ha.

In the treatment of seed, for example by dusting, coating or soaking seeds, application rates of mixture are generally from 1 to 1000 g/100 kg of seed, preferably from 1 to 750 g/100 kg, in particular from 5 to 500 g/100 kg.

The method for controlling harmful fungi is carried out by the separate or joint application of the compounds I and active compounds II or the mixtures of compounds I and active compounds II by spraying or dusting the seeds, the plants or the soils before or after sowing of the plants or before or after emergence of the plants.

The mixtures according to the invention, or the compounds I and active compounds II can be converted into the customary formulations, for example solutions, emulsions, suspensions, dusts, powders, pastes and granules. The use form depends on the particular intended purpose; in each case, it should ensure a fine and even distribution of the compound according to the invention.

The formulations are prepared in a known manner, for example by extending the active compound with solvents and/or carriers, if desired using emulsifiers and dispersants.

Solvents/auxiliaries suitable for this purpose are essentially:

-   -   water, aromatic solvents (for example Solvesso products,         xylene), paraffins (for example mineral oil fractions), alcohols         (for example methanol, butanol, pentanol, benzyl alcohol),         ketones (for example cyclohexanone, gamma-butyrolactone),         pyrrolidones (NMP, NOP), acetates (glycol diacetate), glycols,         fatty acid dimethylamides, fatty acids and fatty acid esters. In         principle, solvent mixtures may also be used,     -   carriers such as ground natural minerals (for example kaolins,         clays, talc, chalk) and ground synthetic minerals (for example         highly disperse silica, silicates); emulsifiers such as         nonionogenic and anionic emulsifiers (for example         polyoxyethylene fatty alcohol ethers, alkylsulfonates and         arylsulfonates) and dispersants such as lignosulfite waste         liquors and methylcellulose.

Suitable surfactants used are alkali metal, alkaline earth metal and ammonium salts of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkyl sulfates, alkylsulfonates, fatty alcohol sulfates, fatty acids and sulfated fatty alcohol glycol ethers, furthermore condensates of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensates of naphthalene or of naphthalenesulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenyl ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenyl polyglycol ethers, tributylphenyl polyglycol ether, tristearylphenyl polyglycol ether, alkylaryl polyether alcohols, alcohol and fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignosulfite waste liquors and methylcellulose.

Substances which are suitable for the preparation of directly sprayable solutions, emulsions, pastes or oil dispersions are mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, for example toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, highly polar solvents, for example dimethyl sulfoxide, N-methylpyrrolidone and water.

Powders, materials for spreading and dustable products can be prepared by mixing or concomitantly grinding the active substances with a solid carrier.

Granules, for example coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active compounds to solid carriers. Examples of solid carriers are mineral earths such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as, for example, ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders and other solid carriers.

Formulations for the treatment of seed may additionally comprise binders and/or gelling agents and, if appropriate, colorants.

In general, the formulations comprise from 0.01 to 95% by weight, preferably from 0.1 to 90% by weight, of the active compounds. The active compounds are employed in a purity of from 90% to 100%, preferably 95% to 100%.

For the treatment of seed, the formulations in question give, after two-to-tenfold dilution, active compound concentrations of from 0.01 to 60% by weight, preferably from 0.1 to 40% by weight, in the ready-to-use preparations.

The following are examples of formulations according to the invention:

-   -   1. Products for dilution with water         A Water-soluble concentrates (SL, LS)         10 parts by weight of a mixture according to the invention are         dissolved in 90 parts by weight of water or in a water-soluble         solvent. As an alternative, wetters or other auxiliaries are         added. The active compound dissolves upon dilution with water.         In this way, a formulation having a content of 10% by weight of         active compound is obtained.         B Dispersible concentrates (DC)         20 parts by weight of a mixture according to the invention are         dissolved in 70 parts by weight of cyclohexanone with addition         of 10 parts by weight of a dispersant, for example         polyvinylpyrrolidone. Dilution with water gives a dispersion.         The active compound content is 20% by weight.         C Emulsifiable concentrates (EC)         15 parts by weight of a mixture according to the invention are         dissolved in 75 parts by weight of xylene with addition of         calcium dodecylbenzenesulfonate and castor oil ethoxylate (in         each case 5 parts by weight). Dilution with water gives an         emulsion. The formulation has an active compound content of 15%         by weight.

D Emulsions (EW, EO, ES)

25 parts by weight of a mixture according to the invention are dissolved in 35 parts by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). This mixture is introduced into 30 parts by weight of water by means of an emulsifying machine (Ultraturrax) and made into a homogeneous emulsion. Dilution with water gives an emulsion. The formulation has an active compound content of 25% by weight.

E Suspensions (SC, OD, FS)

In an agitated ball mill, 20 parts by weight of a mixture according to the invention are comminuted with addition of 10 parts by weight of dispersants and wetters and 70 parts by weight of water or an organic solvent to give a fine active compound suspension. Dilution with water gives a stable suspension of the active compound. The active compound content in the formulation is 20% by weight. F Water-dispersible granules and water-soluble granules (WG, SG) 50 parts by weight of a mixture according to the invention are ground finely with addition of 50 parts by weight of dispersants and wetters and prepared as water-dispersible or water-soluble granules by means of technical appliances (for example extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active compound. The formulation has an active compound content of 50% by weight. G Water-dispersible powders and water-soluble powders (WP, SP, SS, WS) 75 parts by weight of a mixture according to the invention are ground in a rotor-stator mill with addition of 25 parts by weight of dispersants, wetters and silica gel. Dilution with water gives a stable dispersion or solution of the active compound. The active compound content of the formulation is 75% by weight. H Gel formulations In a ball mill, 20 parts by weight of a mixture according to the invention, 10 parts by weight of dispersant, 1 part by weight of gelling agent and 70 parts by weight of water or an organic solvent are ground to give a fine suspension. On dilution with water, a stable suspension having an active compound content of 20% by weight is obtained.

-   -   2. Products to be Applied Undiluted         I Dustable powders (DP, DS)         5 parts by weight of a mixture according to the invention are         ground finely and mixed intimately with 95 parts by weight of         finely divided kaolin. This gives a dustable product having an         active compound content of 5% by weight.

J Granules (GR, FG, GG, MG)

0.5 part by weight of a mixture according to the invention is ground finely and associated with 99.5 parts by weight of carriers. Current methods are extrusion, spray-drying or the fluidized bed. This gives granules to be applied undiluted having an active compound content of 0.5% by weight. K ULV solutions (UL) 10 parts by weight of a mixture according to the invention are dissolved in 90 parts by weight of an organic solvent, for example xylene. This gives a product to be applied undiluted having an active compound content of 10% by weight.

For seed treatment, use is usually made of water-soluble concentrates (LS), suspensions (FS), dustable powders (DS), water-dispersible and water-soluble powders (WS, SS), emulsions (ES), emulsifiable concentrates (EC) and gel formulations (GF). These formulations can be applied to the seed in undiluted form or, preferably, diluted. Application can be carried out prior to sowing.

Preference is given to using FS formulations for seed treatment. Usually, such formulations comprise from 1 to 800 g of active compound/l, from 1 to 200 g of surfactants/l, from 0 to 200 g of antifreeze agents/l, from 0 to 400 g of binder/l, from 0 to 200 g of colorants/1 and solvents, preferably water.

Analogous formulations A to K of the compounds I or an active compound II comprise the respective amount of the individual active compounds. They are usually mixed directly prior to application during dilution to the ready-to-use active compound concentration (tank mix).

The active compound concentrations in the ready-to-use preparations may be varied within relatively wide ranges. In general, they are between 0.0001 and 10%, preferably between 0.01 and 1%.

The active compounds can be used as such, in the form of their formulations or the use forms prepared therefrom, for example in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dustable products, materials for spreading, or granules, by means of spraying, atomizing, dusting, spreading or pouring. The use forms depend entirely on the intended purposes; they are intended to ensure in each case the finest possible distribution of the active compounds according to the invention.

Aqueous use forms can be prepared from emulsion concentrates, pastes or wettable powders (wettable powders, oil dispersions) by adding water. To prepare emulsions, pastes or oil dispersions, the substances, as such or dissolved in an oil or solvent, can be homogenized in water by means of a wetter, tackifier, dispersant or emulsifier. However, it is also possible to prepare concentrates composed of active substance, wetter, tackifier, dispersant or emulsifier and, if appropriate, solvent or oil, and such concentrates are suitable for dilution with water.

The active compounds may also be used successfully in the ultra-low-volume process (ULV), it being possible to apply formulations comprising over 95% by weight of active compound, or even to apply the active compound without additives.

Oils of various types, wetters, adjuvants, herbicides, fungicides, other pesticides, or bactericides may be added to the active compounds, even, if appropriate, not until immediately prior to use (tank mix). These agents may be admixed with the compositions according to the invention in a weight ratio of from 1:100 to 100:1, preferably from 1:10 to 10:1.

Suitable adjuvants in this sense are in particular: organically modified polysiloxanes, for example Break Thru S 240®; alcohol alkoxylates, for example Atplus 245®, Atplus MBA 1303®, Plurafac LF 300® and Lutensol ON 30®; EO/PO block polymers, for example Pluronic RPE 2035® and Genapol B®; alcohol ethoxylates, for example Lutensol XP 80®; and sodium dioctylsulfosuccinate, for example Leophen RA®.

The compounds I and II or the mixtures or the corresponding formulations are applied by treating the harmful fungi, the plants, seeds, soils, areas, materials or spaces to be kept free from them with a fungicidally effective amount of the mixture or, in the case of separate application, of the compounds I and II. Application can be carried out before or after infection by the harmful fungi.

USE EXAMPLES

The fungicidal effect of the compounds and the mixtures was demonstrated by the following tests:

The active compounds amisulbrom, Cu hydroxide, famoxadone, phosphorous acid and zoxamide were used as commercial formulations and diluted with water to the stated concentrations.

The active compounds were separately or jointly prepared as a stock solution comprising 25 mg of active compound which was made up to 10 ml using a mixture of acetone and/or DMSO and the emulsifier Uniperol® EL (wetting agent having emulsifying and dispersing action based on ethoxylated alkylphenols) in a volume ratio of solvent/emulsifier of 99 to 1. The mixture was then made up with water to 100 ml. This stock solution was diluted with the solvent/emulsifier/water mixture described to the concentration of active compound stated below.

Use Example 1 Persistency Against Late Blight on Tomatoes Caused by Phytophthora infestans

Leaves of potted plants of the cultivar “Great beef tomato St. Pierre” were sprayed to runoff point with an aqueous suspension having the concentration of active compound stated below. After 5 days, the leaves were inoculated with an aqueous spore suspension of Phytophthora infestans. The plants were then placed in a water vapor-saturated chamber at temperatures between 18 and 20° C. After 6 days, the late blight on the untreated but infected control plants had developed to such an extent that the infection could be determined visually in %.

The visually determined percentages of infected leaf areas were converted into efficacies in % of the untreated control:

The efficacy (E) is calculated as follows using Abbot's formula:

E=(1−α/β)·100

α corresponds to the fungicidal infection of the treated plants in % and β corresponds to the fungicidal infection of the untreated (control) plants in %

An efficacy of 0 means that the infection level of the treated plants corresponds to that of the untreated control plants; an efficacy of 100 means that the treated plants were not infected.

The expected efficacies of active compound combinations were determined using Colby's formula (Colby, S. R. “Calculating synergistic and antagonistic responses of herbicide combinations”, Weeds, 15, 20-22, 1967) and compared with the observed efficacies.

Colby's formula:

E=x+y−x·y/100

-   E expected efficacy, expressed in % of the untreated control, when     using the mixture of the active compounds A and B at the     concentrations a and b -   x efficacy, expressed in % of the untreated control, when using the     active compound A at the concentration a -   y efficacy, expressed in % of the untreated control, when using the     active compound B at the concentration b

TABLE A Individual active compounds Concentration of active Efficacy in % compound in the spray of the untreated No. Active compound liquor [ppm] control 1 control (untreated) — (90% infection) 2 Table 1; I-18 16 11 3 Table 1; I-25 16 0 4 Table 1; I-28 63 44 5 Table 1; I-113 16 22 6 Table 1; I-120 16 33 7 Table 1; I-180 63 33 16 0 8 Table 1; I-245 4 0 9 metiram 63 33 16 0 10 cyazofamid 4 33 11 metalaxyl 63 56 16 33 12 dimethomorph 4 33

TABLE B Mixtures according to the invention of the active compounds from Table 1 Mixture of active compounds Concentration Calculated No. Mixing ratio Observed efficacy efficacy*) 13 I-18 + cyazofamid 97 41 16 + 4 ppm 4:1 14 I-18 + dimethomorph 89 41 16 + 4 ppm 4:1 15 I-25 + metiram 67 33 63 + 16 ppm 4:1 16 I-25 + metalaxyl 83 56 16 + 63 ppm 1:4 17 I-28 + metiram 89 44 63 + 16 ppm 4:1 18 I-28 + metalaxyl 83 63 63 + 16 ppm 4:1 19 I-113 + metiram 67 48 16 + 63 ppm 1:4 20 I-113 + cyazofamid 67 48 16 + 4 ppm 4:1 21 I-113 + metalaxyl 83 65 16 + 63 ppm 1:4 22 I-113 + dimethomorph 67 48 16 + 4 ppm 4:1 23 I-120 + cyazofamid 99 56 16 + 4 ppm 4:1 24 I-120 + metalaxyl 94 70 16 + 63 ppm 1:4 25 I-180 + metiram 89 33 16 + 63 ppm 1:4 26 I-180 + metiram 99 56 63 + 63 ppm 1:1 27 I-180 + cyazofamid 72 33 4 + 4 ppm 1:1 28 I-180 + cyazofamid 97 33 16 + 4 ppm 4:1 29 I-180 + metalaxyl 94 56 16 + 63 ppm 1:4 30 I-180 + dimethomorph 83 33 4 + 4 ppm 1:1 31 I-180 + dimethomorph 97 33 16 + 4 ppm 4:1 32 I-245 + metalaxyl 92 33 4 + 16 ppm 1:4 *)efficacy calculated using Colbys formula

Use Example 2 Activity Against Late Blight on Tomatoes Caused by Phytophthora infestans, Protective Treatment

Leaves of potted tomato plants were sprayed to runoff point with an aqueous suspension having the active compound concentration stated below. After seven days, the leaves were infected with an aqueous sporangia suspension of Phytophthora infestans. The plants were then placed in a water vapor-saturated chamber at temperatures between 18 and 20° C. After 6 days, the late blight on the untreated but infected control plants had developed to such an extent that the infection could be determined visually in %.

Evaluation was carried out analogously to example 1.

Calculated Active compound/ Observed activity active compound Conc. activity according to No. combination (mg/l) Ratio (%) Colby (%) 33 control — 90% (infection) 34 Tab. 1; I-110 [I-110]  4 11 35 Cu(OH)₂ 63 11 36 mancozeb 63 11 37 phosphorous acid 63 33 disodium salt (Na₂HPO₃) 38 [I-110] + Cu(OH)₂ 4 + 63 1:4 56 21 39 [I-110] + mancozeb 4 + 63 1:4 56 21 40 [I-110] + Na₂HPO₃ 4 + 63  1:16 67 41

Use Example 3 Activity Against Peronospora of Grapevines Caused by Plasmopara viticola

Leaves of potted grapevines were sprayed to runoff point with an aqueous suspension having the active compound concentration stated below. After three days, the undersides of the leaves were inoculated with an aqueous sporangia suspension of Plasmopara viticola. The vines were then initially placed in a water vapor-saturated chamber at 24° C. for 24 hours and then in a greenhouse at temperatures between 20 and 30° C. for 5 days. After this time, the plants were again placed in a humid chamber for 16 hours to promote sporangiophore eruption. The extent of the development of the infection on the undersides of the leaves was then determined visually.

Evaluation was carried out analogously to example 1.

Calculated activity Active compound/ Observed according active compound Conc. activity to No. combination (mg/l) Ratio (%) Colby (%) 41 control 90% (infection) 42 Tab. 1; I-110 16 56 [I-110] 4 0 0.25 0 43 [B-6] 16 0 44 amidosulbrom 4 22 45 famoxadone 4 0 46 iprovalicarb 4 0 47 [E-7] 0.25 0 48 zoxamide 4 11 49 ethaboxam 0.25 33 50 [I-110] + [B-6] 16 + 16 1:1 78 56 51 [I-110] + 4 + 4 1:1 94 22 amidosulbrom 52 [I-110] + 4 + 4 1:1 78 0 famoxadone 53 [I-110] + 4 + 4 1:1 44 0 iprovalicarb 54 [I-110] + [E-7] 0.25 + 0.25 1:1 56 0 55 [I-110] + zoxamide 4 + 4 1:1 56 11 56 [I-110] + 0.25 + 0.25 1:1 56 33 ethaboxam

Use Example 4 Activity Against Peronospora of Grapevines Caused by Plasmopara viticola

Leaves of potted grapevines were sprayed to runoff point with an aqueous suspension having the active compound concentration stated below. After seven days, the undersides of the leaves were inoculated with an aqueous sporangia suspension of Plasmopara viticola. The vines were then initially placed in a water vapor-saturated chamber at 24° C. for 24 hours and then in a greenhouse at temperatures between 20 and 30° C. for 5 days. After this time, the plants were again placed in a humid chamber for 16 hours to promote sporangiophore eruption. The extent of the development of the infection on the undersides of the leaves was then determined visually.

Evaluation was carried out analogously to example 1.

Calculated Active compound/ activity active compound Conc. Observed according to No. combination (mg/l) Ratio activity (%) Colby (%) 57 control 90% (infection) 58 Tab. 1; I-110 16 0 [I-110]  4 0 59 cymoxanil 16 33 60 dithianon 16 0 61 dimethomorph 16 67 62 [I-110] + cymoxanil 16 + 16 1:1 56 33 63 [I-110] + dithianon  4 + 16 1:4 44 0 64 [I-110] +  4 + 16 1:4 97 67 dimethomorph

Microtests

The active compounds were formulated separately as a stock solution of a concentration of 10 000 ppm in DMSO.

The active compounds fluazinam, pyraclostrobin, copper hydroxide, flubenthiavalicarb, phosphorous acid, dodemorph, zoxamide, amidosulbrom and trifloxystrobin were used as commercial formulations and diluted with water to the stated concentrations.

Use Example 5 Activity Against the Late Blight Pathogen Phytophthora infestans in the Microtiter Test

The stock solution is pipetted onto a microtiter plate (MTP) and diluted to the stated active compound concentration using a pea juice-based aqueous nutrient medium for fungi. An aqueous zoospore suspension of Phytophthora infestans was then added. The plates were placed in a water vapor-saturated chamber at temperatures of 18° C. Using an absorption photometer, the MTPs were measured at 405 nm on day 7 after the inoculation.

The measured parameters were compared to the growth of the active compound-free control variant and the fungus- and active compound-free blank value to determine the relative growth in % of the pathogens in the individual active compounds.

Calculated activity Active compound/active Observed according to No. compound combination Conc. (mg/l) Ratio activity (%) Colby (%) 65 Tab. 1; I-9 [I-9] 0.25 7 0.063 6 0.016 1 66 Tab. 1; I-18 [I-18] 1 45 0.25 16 0.063 6 67 Tab. 1; I-25 [I-25] 1 13 0.25 5 0.063 4 68 Tab. 1; I-28 [I-28] 1 24 0.25 14 0.063 0 0.016 0 69 Tab. 1; I-98 [I-98] 4 22 1 16 0.25 6 0.063 5 70 Tab. 1; I-101 [I-101] 4 9 0.25 3 71 Tab. 1; I-110 [I-110] 1 59 0.25 5 0.063 3 0.016 1 72 Tab. 1; I-113 [I-113] 4 36 0.25 3 73 Tab. 1; I-120 [I-120] 0.25 6 0.063 2 0.016 0 74 Tab. 1; I-180 [I-180] 1 17 0.25 8 0.063 2 0.016 0 75 Tab. 1; I-245 [I-245] 0.25 12 0.063 0 0.016 0 76 Tab. 1; I-290 [I-290] 4 3 0.25 0 0.063 0 77 fosetyl-Al 4 6 78 Cu(OH)₂ 4 2 79 folpet 1 6 80 captan 1 12 81 maneb 1 6 82 metiram 16 49 4 9 83 metalaxyl 4 9 1 6 84 flubenthiavalicarb 0.25 68 85 Na₂HPO₃ 4 6 86 Cu₂Cl(OH)₃ 16 18 87 cyprodinil 4 10 88 prochloraz 16 6 89 fenamidone 0.063 40 90 enestroburin 1 35 91 benalaxyl 4 13 92 oxadixyl 16 17 4 2 1 0 93 ofurace 16 19 4 0 94 difenoconazole 4 24 95 tebuconazole 16 9 4 10 1 8 96 propiconazole 16 12 4 11 1 1 97 cyproconazole 4 9 98 flusilazole 4 11 1 0 99 fluquinconazole 4 0 1 0 100 boscalid 4 17 1 2 101 metrafenone 4 2 102 [D-8] 1 43 103 vinclozolin 16 0 104 [B-6] 0.25 10 105 trifloxystrobin 1 46 0.25 33 106 fluazinam 0.25 9 107 mandipropamid 0.25 40 0.063 10 108 fluoxastrobin 0.025 2 0.063 1 109 azoxystrobin 0.063 21 110 pyraclostrobin 0.063 59 0.016 14 111 [I-9] + fenamidone 0.016 + 0.063 1:4 63 41 112 [I-9] + enestroburin 0.25 + 1   1:4 92 40 113 [I-9] + mandipropamid 0.25 + 0.25 1:1 95 44 114 [I-9] + fluoxastrobin 0.25 + 0.25 1:1 91 9 115 [I-9] + pyraclostrobin 0.063 + 0.016 4:1 40 19 116 [I-18] + cyprodinil 1 + 4 1:4 83 59 117 [I-18] + enestroburin 0.25 + 1   1:4 91 45 118 [I-18] + benalaxyl 1 + 4 1:4 97 52 119 [I-18] + oxadixyl 1 + 4 1:4 96 46 120 [I-18] + ofurace 1 + 4 1:4 99 45 121 [I-18] + difenoconazole 1 + 4 1:4 89 58 122 [I-18] + tebuconazole 1 + 4 1:4 94 50 123 [I-18] + propiconazole 1 + 4 1:4 96 51 124 [I-18] + mandipropamid 0.25 + 0.25 1:1 96 50 125 [I-18] + fluoxastrobin 0.25 + 0.25 1:1 92 18 126 [I-18] + azoxystrobin 0.063 + 0.063 1:1 49 26 127 [I-18] + pyraclostrobin 0.063 + 0.016 4:1 39 19 128 [I-25] + fosetyl-Al 1 + 4 1:4 69 18 129 [I-25] + Cu(OH)₂ 1 + 4 1:4 95 15 130 [I-25] + metiram 1 + 4 1:4 98 21 131 [I-25] + metalaxyl 1 + 4 1:4 78 21 132 [I-25] + Na₂HPO₃ 1 + 4 1:4 74 15 133 [I-25] + enestroburin 0.25 + 1   1:4 94 38 134 [I-25] + cyproconazole 1 + 4 1:4 75 21 135 [I-25] + flusilazole 1 + 4 1:4 89 23 136 [I-25] + fluquinconazole 1 + 4 1:4 94 13 137 [I-25] + boscalid 1 + 4 1:4 95 28 138 [I-25] + metrafenone 1 + 4 1:4 90 14 139 [I-25] + [B-6] 0.25 + 0.25 1:1 58 15 140 [I-25] + trifloxystrobin 1 + 1 1:1 79 53 141 [I-25] + pyraclostrobin 0.063 + 0.016 4:1 95 17 142 [I-28] + Cu(OH)₂ 1 + 4 1:4 98 26 143 [I-28] + flubenthiavalicarb 0.063 + 0.25  1:4 99 68 144 [I-28] + fenamidone 0.016 + 0.063 1:4 63 40 145 [I-28] + cyproconazole 1 + 4 1:4 69 31 146 [I-28] + flusilazole 1 + 4 1:4 95 33 147 [I-28] + fluquinconazole 1 + 4 1:4 89 24 148 [I-28] + boscalid 1 + 4 1:4 89 37 149 [I-28] + metrafenone 1 + 4 1:4 78 26 150 [I-28] + fluazinam 0.25 + 0.25 1:1 67 22 151 [I-28] + mandipropamid 0.063 + 0.063 1:1 58 10 152 [I-28] + fluoxastrobin 0.25 + 0.25 1:1 95 16 153 [I-28] + azoxystrobin 0.063 + 0.063 1:1 77 21 154 [I-28] + pyraclostrobin 0.063 + 0.016 4:1 47 14 155 [I-98] + Cu₂Cl(OH)₃  4 + 16 1:4 99 36 156 [I-98] + enestroburin 0.25 + 1   1:4 87 38 157 [I-98] + tebuconazole  4 + 16 1:4 69 29 158 [I-98] + propiconazole  4 + 16 1:4 83 31 159 [I-98] + fluquinconazole 1 + 4 1:4 65 16 160 [I-98] + metrafenone 1 + 4 1:4 47 17 161 [I-98] + fluoxastrobin 0.063 + 0.063 1:1 93 4 162 [I-98] + azoxystrobin 0.063 + 0.063 1:1 48 25 163 [I-101] + maneb 0.25 + 1   1:4 57 11 164 [I-101] + Cu₂Cl(OH)₃  4 + 16 1:4 75 25 165 [I-101] + prochloraz  4 + 16 1:4 81 14 166 [I-101] + enestroburin 0.25 + 1   1:4 59 37 167 [I-101] + vinclozolin  4 + 16 1:4 48 9 168 [I-101] + mandipropamid 0.25 + 0.25 1:1 66 42 169 [I-101] + fluoxastrobin 0.25 + 0.25 1:1 91 5 170 [I-101] + pyraclostrobin  0.25 + 0.063 4:1 87 60 171 [I-110] + metalaxyl 0.25 + 1   1:4 50 11 172 [I-110] + captan 0.25 + 1   1:4 64 16 173 [I-110] + metiram 1 + 4 1:4 84 63 174 [I-110] + flubenthiavalicarb 0.063 + 0.25  1:4 98 69 175 [I-110] + fenamidone 0.016 + 0.063 1:4 72 41 176 [I-110] + enestroburin 0.25 + 1   1:4 99 38 177 [I-110] + oxadixyl 0.25 + 1   1:4 48 5 178 [I-110] + tebuconazole 0.25 + 1   1:4 88 13 179 [I-110] + propiconazole 0.25 + 1   1:4 75 6 180 [I-110] + cyproconazole 1 + 4 1:4 76 62 181 [I-110] + flusilazole 1 + 4 1:4 84 63 182 [I-110] + boscalid 0.25 + 1   1:4 73 7 183 [I-110] + [B-6] 0.25 + 0.25 1:1 48 15 184 [I-110] + trifloxystrobin 0.25 + 0.25 1:1 66 36 185 [I-110] + mandipropamid 0.63 + 0.63 1:1 76 12 186 [I-110] + fluoxastrobin 0.63 + 0.63 1:1 93 4 187 [I-110] + azoxystrobin 0.63 + 0.63 1:1 85 23 188 [I-110] + pyraclostrobin 0.63 + 0.63 1:1 55 16 189 [I-113] + prochloraz  4 + 16 1:4 99 40 190 [I-113] + oxadixyl  4 + 16 1:4 63 46 191 [I-113] + ofurace  4 + 16 1:4 68 48 192 [I-113] + propiconazole  4 + 16 1:4 93 43 193 [I-113] + fluquinconazole 1 + 4 1:4 71 7 194 [I-113] + trifloxystrobin 0.25 + 0.25 1:1 51 35 195 [I-113] + mandipropamid 0.25 + 0.25 1:1 93 42 196 [I-113] + fluoxastrobin 0.25 + 0.25 1:1 95 5 197 [I-113] + pyraclostrobin  0.25 + 0.063 4:1 96 60 198 [I-120] + captan 0.25 + 1   1:4 89 17 199 [I-120] + benthiavalicarb 0.063 + 0.25  1:4 98 64 200 [I-120] + fenamidone 0.016 + 0.063 1:4 72 40 201 [I-120] + flusilazole 0.25 + 1   1:4 89 6 202 [I-120] + fluquinconazole 0.25 + 1   1:4 71 6 203 [I-120] + [D-8] 0.25 + 1   1:4 79 46 204 [I-120] + fluoxastrobin 0.063 + 0.063 1:1 95 3 205 [I-120] + azoxystrobin 0.063 + 0.063 1:1 92 23 206 [I-120] + pyraclostrobin 0.063 + 0.016 4:1 54 16 207 [I-180] + metiram 1 + 4 1:4 57 24 208 [I-180] + flubenthiavalicarb 0.063 + 0.25  1:4 95 69 209 [I-180] + fenamidone 0.016 + 0.063 1:4 62 40 210 [I-180] + enestroburin 0.25 + 1   1:4 96 40 211 [I-180] + benalaxyl 1 + 4 1:4 70 28 212 [I-180] + oxadixyl 1 + 4 1:4 95 18 213 [I-180] + ofurace 1 + 4 1:4 92 17 214 [I-180] + difenoconazole 1 + 4 1:4 86 37 215 [I-180] + tebuconazole 1 + 4 1:4 97 25 216 [I-180] + propiconazole 1 + 4 1:4 88 26 217 [I-180] + [B-6] 0.25 + 0.25 1:1 40 16 218 [I-180] + trifloxystrobin 0.25 + 0.25 1:1 60 38 219 [I-180] + mandipropamid 0.063 + 0.063 1:1 39 11 220 [I-180] + azoxystrobin 0.063 + 0.063 1:1 52 22 221 [I-245] + fenamidone 0.016 + 0.063 1:4 73 40 222 [I-245] + fluazinam 0.25 + 0.25 1:1 51 20 223 [I-245] + mandipropamid 0.063 + 0.063 1:1 51 10 224 [I-245] + fluoxastrobin 0.25 + 0.25 1:1 96 14 225 [I-245] + azoxystrobin 0.063 + 0.063 1:1 51 21 226 [I-245] + pyraclostrobin  0.25 + 0.063 4:1 94 64 227 [I-290] + folpet 0.25 + 1   1:4 45 6 228 [I-290] + metiram  4 + 16 1:4 80 51 229 [I-290] + flubenthiavalicarb 0.063 + 0.25  1:4 89 68 230 [I-290] + [B-6] 0.25 + 0.25 1:1 30 10 231 [I-290] + fluoxastrobin 0.25 + 0.25 1:1 95 2

Use Example 6 Activity Against the Gray Mold Pathogen Botrytis cinerea in the Microtiter Test

The stock solution is pipetted onto a microtiter plate (MTP) and diluted to the stated active compound concentration using a malt-based aqueous nutrient medium for fungi. An aqueous spore suspension of Botrytis cinerea was then added. The plates were placed in a water vapor-saturated chamber at temperatures of 18° C. Using an absorption photometer, the MTPs were measured at 405 nm on day 7 after the inoculation.

Evaluation was carried out analogously to example 5.

Calculated activity Active compound/active Observed according to No. compound combination Conc. (mg/l) Ratio activity (%) Colby (%) 232 Tab. 1; I-9 [I-9] 0.25 8 233 Tab. 1; I-18 [I-18] 16 11 1 8 0.063 6 234 Tab. 1; I-25 [I-25] 0.25 5 235 Tab. 1; I-28 [I-28] 4 0 236 Tab. 1; I-98 [I-98] 1 5 0.25 4 237 Tab. 1; I-101 [I-101] 1 1 238 Tab. 1; I-110 [I-110] 0.25 18 0.063 8 239 Tab. 1; I-120 [I-120] 16 15 1 9 0.063 0 240 Tab. 1; I-180 [I-180] 0.25 13 0.016 3 241 Tab. 1; I-245 [I-245] 0.25 0 242 Tab. 1; I-290 [I-290] 1 4 243 chlorothalonil 1 55 244 folpet 1 2 245 CuSO₄ 63 0 246 thiophanate-methyl 0.25 12 247 tebuconazole 0.25 50 248 flusilazole 0.25 43 249 fluquinconazole 0.063 22 250 prothioconazole 4 48 251 vinclozolin 1 21 252 zoxamide 1 55 253 [B-6] 16 53 254 fluazinam 0.063 50 255 [I-9] + chlorothalonil 0.25 + 1   1:4 91 59 256 [I-18] + thiophanate-methyl 0.063 + 0.25  1:4 35 17 257 [I-18] + flusilazole 0.063 + 0.25  1:4 76 46 258 [I-18] + prothioconazole 1 + 4 1:4 99 52 259 [I-18] + [B-6] 16 + 16 1:1 81 58 260 [I-25] + chlorothalonil 0.25 + 1   1:4 99 57 261 [I-25] + folpet 0.25 + 1   1:4 61 7 262 [I-28] + maneb  4 + 16 1:4 69 15 263 [I-98] + prothioconazole 1 + 4 1:4 90 51 264 [I-98] + vinclozolin 0.25 + 1   1:4 68 25 265 [I-101] + zoxamide 1 + 1 1:1 69 55 266 [I-110] + chlorothalonil 0.25 + 1   1:4 93 63 267 [I-110] + folpet 0.25 + 1   1:4 50 20 268 [I-110] + vinclozolin 0.25 + 1   1:4 81 35 269 [I-110] + fluazinam 0.063 + 0.063 1:1 77 54 270 [I-120] + CuSO₄ 16 + 63 1:4 53 15 271 [I-120] + tebuconazole 0.063 + 0.25  1:4 67 50 272 [I-120] + prothioconazole 1 + 4 1:4 94 53 273 [I-180] + chlorothalonil 0.25 + 1   1:4 92 61 274 [I-180] + folpet 0.25 + 1   1:4 75 15 275 [I-180] + fluquinconazole 0.016 + 0.063 1:4 100 24 276 [I-180] + vinclozolin 0.25 + 1   1:4 89 31 277 [I-180] + carbendazim 0.016 + 0.016 1:1 36 15 278 [I-245] + vinclozolin 0.25 + 1   1:4 55 21 279 [I-290] + prothioconazole 1 + 4 1:4 88 51

Use Example 7 Activity Against the Rice Blast Pathogen Pyricularia oryzae in the Microtiter Test

The stock solutions were mixed according to the ratio, pipetted onto a microtiter plate (MTP) and diluted to the stated active compound concentration using a malt-based aqueous nutrient medium for fungi. An aqueous spore suspension of Pyricularia oryzae was then added. The plates were placed in a water vapor-saturated chamber at temperatures of 18° C. Using an absorption photometer, the MTPs were measured at 405 nm on day 7 after the inoculation.

Evaluation was carried out analogously to example 5.

Calculated activity Active compound/active Conc. Observed according to No. compound combination (mg/l) Ratio activity (%) Colby (%) 280 Tab. 1; I-9 [I-9] 1 13 0.25 7 281 Tab. 1; I-18 [I-18] 16 29 4 18 1 15 0.25 15 282 Tab. 1; I-25 [I-25] 1 24 283 Tab. 1; I-28 [I-28] 1 13 0.25 12 284 Tab. 1; I-98 [I-98] 16 43 4 15 1 0 0.25 0 285 Tab. 1; I-101 [I-101] 16 25 4 16 1 15 286 Tab. 1; I-110 [I-110] 16 8 287 Tab. 1; I-113 [I-113] 4 7 288 Tab. 1; I-120 [I-120] 16 25 289 Tab. 1; I-180 [I-180] 1 15 290 Tab. 1; I-245 [I-245] 16 23 0.25 10 291 fosetyl-Al 16 49 292 captan 1 44 293 maneb 4 32 294 metiram 4 26 295 metalaxyl 63 2 296 CuSO₄ 63 0 297 cyproconazole 4 54 298 fluquinconazole 4 0 299 prothioconazole 4 11 300 boscalid 63 12 301 metrafenone 63 42 302 dodemorph 16 72 303 cymoxanil 16 12 304 carbendazim 0.25 20 305 iprodione 4 46 306 cyazofamid 4 23 307 [I-9] + captan 0.25 + 1   1:4 85 48 308 [I-9] + cyproconazole 1 + 4 1:4 79 60 309 [I-9] + fluquinconazole 1 + 4 1:4 39 13 310 [I-9] + prothioconazole 1 + 4 1:4 91 23 311 [I-18] + captan 0.25 + 1   1:4 88 52 312 [I-18] + maneb 1 + 4 1:4 57 42 313 [I-18] + cyproconazole 1 + 4 1:4 86 61 314 [I-18] + fluquinconazole 1 + 4 1:4 47 15 315 [I-18] + iprodione 4 + 4 1:1 89 55 316 [I-18] + cyazofamid 16 + 4  4:1 61 45 317 [I-25] + maneb 1 + 4 1:4 80 49 318 [I-25] + prothioconazole 1 + 4 1:4 100 33 319 [I-28] + captan 0.25 + 1   1:4 73 51 320 [I-28] + prothioconazole 1 + 4 1:4 50 23 321 [I-98] + maneb 1 + 4 1:4 58 32 322 [I-98] + metiram 1 + 4 1:4 47 26 323 [I-98] + metalaxyl 16 + 63 1:4 63 44 324 [I-98] + boscalid 16 + 63 1:4 65 49 325 [I-98] + dodemorph  4 + 16 1:4 98 76 326 [I-98] + cymoxanil 16 + 16 1:1 79 50 327 [I-98] + carbendazim 0.25 + 0.25 1:1 75 20 328 [I-98] + cyazofamid 16 + 4  4:1 93 56 329 [I-101] + fosetyl-Al  4 + 16 1:4 74 59 330 [I-101] + CuSO₄ 16 + 63 1:4 56 25 331 [I-101] + fluquinconazole 1 + 4 1:4 46 15 332 [I-101] + prothioconazole 1 + 4 1:4 64 25 333 [I-101] + iprodione 4 + 4 1:1 89 54 334 [I-101] + cyazofamid 4 + 1 4:1 91 22 335 [I-110] + metrafenone 16 + 63 1:4 100 47 336 [I-113] + iprodione 4 + 4 1:1 70 49 337 [I-120] + cyazofamid 16 + 4  4:1 64 42 338 [I-180] + prothioconazole 1 + 4 1:4 92 24 339 [I-245] + captan 0.25 + 1   1:4 90 49 340 [I-245] + metrafenone 16 + 63 1:4 100 55

Use Example 8 Activity Against the Speckled Leaf Blotch Pathogen Septoria tritici in the Microtiter Test

The stock solution was mixed according to the ratio, pipetted onto a microtiter plate (MTP) and diluted to the stated active compound concentration using a malt-based aqueous nutrient medium for fungi. An aqueous spore suspension of Septoria tritici was then added. The plates were placed in a water vapor-saturated chamber at temperatures of 18° C. Using an absorption photometer, the MTPs were measured at 405 nm on day 7 after the inoculation.

Evaluation was carried out analogously to example 5.

Calculated activity Active compound/ Observed according active compound activity to No. combination Conc. (mg/l) Ratio (%) Colby (%) 341 Tab. 1; I-120 0.063 0 [I-120] 342 prohexadione-Ca 0.25 5 343 [I-120] + 0.063 + 0.25 1:4 44 5 prohexadione-Ca

The test results show that, by virtue of the synergism, the mixtures according to the invention are considerably more effective than had been predicted using Colby's formula. 

1. A fungicidal mixture comprising, as active components: 1) an azolopyrimidinylamine of formula I

wherein: R¹ is C₃-C₁₂-alkyl, C₂-C₁₂-alkenyl, C₅-C₁₂-alkoxyalkyl, C₃-C₆-cycloalkyl, phenyl or phenyl-C₁-C₄-alkyl; R² is C₁-C₁₂-alkyl, C₂-C₁₂-alkenyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy-C₁-C₄-alkyl; where the aliphatic chains in R¹ and/or R² may be substituted by one to four identical or different groups R^(a): R^(a) is halogen, cyano, hydroxyl, mercapto, C₁-C₁₀-alkyl, C₁-C₁₀-haloalkyl, C₃-C₈-cycloalkyl, C₂-C₁₀-alkenyl, C₂-C₁₀-alkynyl, C₁-C₆-alkoxy, C₁-C₆-alkylthio, C₁-C₆-alkoxy-C₁-C₆-alkyl or NR^(A)R^(B); R^(A), R^(B) are hydrogen and C₁-C₆-alkyl; where the cyclic groups in R¹ and/or R^(a) may be substituted by one to four groups R^(b): R^(b) is halogen, cyano, hydroxyl, mercapto, nitro, NR^(A)R^(B), C₁-C₁₀-alkyl, C₁-C₆-haloalkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl or C₁-C₆-alkoxy; R³ is hydrogen, halogen, cyano, NR^(A)R^(B), hydroxyl, mercapto, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₃-C₈-cycloalkyl, C₁-C₆-alkoxy, C₁-C₆-alkylthio, C₃-C₈-cycloalkoxy, C₃-C₈-cycloalkylthio, carboxyl, formyl, C₁-C₁₀-alkylcarbonyl, C₁-C₁₀-alkoxycarbonyl, C₂-C₁₀-alkenyloxycarbonyl, C₂-C₁₀-alkynyloxycarbonyl, phenyl, phenoxy, phenylthio, benzyloxy, benzylthio, or C₁-C₆-alkyl-S(O)_(m)—; m is 0, 1 or 2; A is CR³ or N; and 2) at least one active compound II selected from the group consisting of: A) bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, enilconazole, epoxiconazole, fluquinconazole, fenbuconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, penconazole, propiconazole, prothioconazole, simeconazole, triadimefon, triadimenol, tebuconazole, tetraconazole, triticonazole, prochloraz, pefurazoate, imazalil, triflumizole, cyazofamid, benomyl, carbendazim, thiabendazole, fuberidazole, ethaboxam, etridiazole, hymexazole; B) azoxystrobin, dimoxystrobin, enestroburin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, trifloxystrobin, methyl (2-chloro-5-[1-(3-methylbenzyloxyimino)ethyl]benzyl)carbamate, methyl (2-chloro-5-[1-(6-methylpyridin-2-ylmethoxyimino)ethyl]benzyl)carbamate, methyl 2-(ortho-((2,5-dimethylphenyloxymethylene)phenyl)-3-methoxyacrylate; C) carboxin, benalaxyl, boscalid, fenhexamid, flutolanil, furametpyr, mepronil, metalaxyl, mefenoxam, ofurace, oxadixyl, oxycarboxin, penthiopyrad, thifluzamide, tiadinil, N-(4′-bromobiphenyl-2-yl)-4-difluoromethyl-2-methylthiazole-5-carboxamide, N-(4′-trifluoromethylbiphenyl-2-yl)-4-difluoromethyl-2-methylthiazole-5-carboxamide, N-(4′-chloro-3′-fluorobiphenyl-2-yl)-4-difluoromethyl-2-methylthiazole-5-carboxamide, N-(3′,4′-dichloro-4-fluorobiphenyl-2-yl)-3-difluoromethyl-1-methylpyrazole-4-carboxamide, N-(3′,4′-dichloro-5-fluorobiphenyl-2-yl)-3-difluoromethyl-1-methylpyrazole-4-carboxamide, 3,4-dichloro-N-(2-cyanophenyl)isothiazol-5-carboxamide, dimethomorph, flumorph; flumetover, fluopicolide (picobenzamid), zoxamide, carpropamid, diclocymet, mandipropamid; N-(2-{4-[3-(4-chlorophenyl)prop-2-ynyloxy]-3-methoxyphenyl}ethyl)-2-methanesulfonylamino-3-methylbutyramide, N-(2-{4-[3-(4-chlorophenyl)-prop-2-ynyloxy]-3-methoxyphenyl}ethyl)-2-ethanesulfonylamino-3-methylbutyramide; D) fluazinam, pyrifenox, bupirimate, cyprodinil, fenarimol, ferimzone, mepanipyrim, nuarimol, pyrimethanil triforine, fenpiclonil, fludioxonil aldimorph, dodemorph, fenpropimorph, tridemorph, fenpropidin, iprodione, procymidone, vinclozolin, famoxadone, fenamidone, octhilinone, probenazole, anilazine, diclomezine, pyroquilon, proquinazid, tricyclazole, amisulbrom, 5-chloro-7-(4-methylpiperidin-1-yl)-6-(2,4,6-trifluorophenyl)-[1,2,4]triazolo[1,5-a]pyrimidine, 2-butoxy-6-iodo-3-propylchromen-4-one, acibenzolar-5-methyl, captafol, captan, dazomet, folpet, fenoxanil, quinoxyfen, 3-[5-(4-chlorophenyl)-2,3-dimethylisoxazolidin-3-yl]pyridine; E) mancozeb, maneb, metam, metiram, ferbam, propineb, thiram, zineb, ziram, diethofencarb, iprovalicarb, flubenthiavalicarb, propamocarb, and methyl 3-(4-chlorophenyl)-3-(2-isopropoxycarbonylamino-3-methylbutyrylamino)propanoate; and F) dodine, iminoctadine, guazatine; kasugamycin, streptomycin, polyoxine, validamycin A; binapacryl, dinocap, dinobuton; dithianon, isoprothiolane; fentin salts; edifenphos, iprobenfos, fosetyl, fosetyl-aluminum, phosphorous acid and its salts, pyrazophos, tolclofos-methyl; chlorothalonil, dichlofluanid, flusulfamide, hexachlorobenzene, phthalide, pencycuron, quintozene, thiophanate-methyl, tolylfluanid; Bordeaux mixture, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, sulfur; cyflufenamid, cymoxanil, dimethirimol, ethirimol, furalaxyl, metrafenone, spiroxamine; prohexadione and its salts, trinexapac-ethyl, chlormequat, mepiquat-chloride, diflufenzopyr; wherein the azolopyrimidinylamine of formula I and the at least one active compound II of the mixture are present in a synergistically effective amount.
 2. The fungicidal mixture of claim 1, wherein the weight ratio of the azolopyrimidinylamine of formula I and the at least one active compound of formula II is from 100:1 to 1:100.
 3. The fungicidal mixture of claim 1, wherein the azolopyrimidinylamine of formula I is of the formula IA

wherein R¹ is C₃-C₁₂-alkyl, C₅-C₁₂-alkoxyalkyl, phenyl or phenyl-C₁-C₄-alkyl, where phenyl may be substituted by one to three groups R^(b); R² is C₁-C₁₂-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy-C₁-C₄-alkyl; R³ is hydrogen or NH₂.
 4. The fungicidal mixture of claim 1, wherein the azolopyrimidinylamine of formula I is selected from the group consisting of 6-(3,4-dichloro-phenyl)-5-methyl-[1,2,4]triazolo[1,5-a]pyrimidin-7-ylamine; 6-(4-tert-butylphenyl)-5-methyl-[1,2,4]triazolo[1,5-a]pyrimidin-7-ylamine; 5-methyl-6-(3,5,5-trimethyl-hexyl)-[1,2,4]triazolo[1,5-a]pyrimidin-7-ylamine; 5-methyl-6-octyl-[1,2,4]triazolo[1,5-a]pyrimidin-7-ylamine; 6-methyl-5-octyl-[1,2,4]triazolo[1,5-a]pyrimidin-7-ylamine; 6-ethyl-5-octyl-[1,2,4]triazolo[1,5-a]pyrimidin-7-ylamine; 5-ethyl-6-octyl-[1,2,4]triazolo[1,5-a]pyrimidin-7-ylamine; 5-ethyl-6-(3,5,5-trimethyl-hexyl)-[1,2,4]triazolo[1,5-a]pyrimidin-7-ylamine; 6-octyl-5-propyl-[1,2,4]triazolo[1,5-a]pyrimidin-7-ylamine; 5-methoxymethyl-6-octyl-[1,2,4]triazolo[1,5-a]pyrimidin-7-ylamine; 6-octyl-5-trifluormethyl-[1,2,4]triazolo[1,5-a]pyrimidin-7-ylamine and 5-trifluoromethyl-6-(3,5,5-trimethyl-hexyl)-[1,2,4]triazolo[1,5-a]pyrimidin-7-ylamine.
 5. The fungicidal mixture of claim 1, wherein the at least one active compound II is selected from the group A, C or E.
 6. The fungicidal mixture of claim 1, wherein the at least one active compound II is selected from the group B, D or F.
 7. The fungicidal mixture of claim 1, wherein the mixture comprises the azolopyrimidinylamine of formula I and two active compounds II, wherein each active compound II is independently selected from the group A, B, C, D, E or F.
 8. A composition comprising a liquid or solid carrier; and a mixture of 1) an azolopyrimidinylamine of formula I

wherein: R¹ is C₃-C₁₂-alkyl, C₂-C₁₂-alkenyl, C₅-C₁₂-alkoxyalkyl, C₃-C₆-cycloalkyl, phenyl or phenyl-C₁-C₄-alkyl; R² is C₁-C₁₂-alkyl, C₂-C₁₂-alkenyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy-C₁-C₄-alkyl; where the aliphatic chains in R¹ and/or R² may be substituted by one to four identical or different groups R^(a): R^(a) is halogen, cyano, hydroxyl, mercapto, C₁-C₁₀-alkyl, C₁-C₁₀-haloalkyl, C₃-C₈-cycloalkyl, C₂-C₁₀-alkenyl, C₂-C₁₀-alkynyl, C₁-C₆-alkoxy, C₁-C₆-alkylthio, C₁-C₆-alkoxy-C₁-C₆-alkyl or NR^(A)R^(B); R^(A), R^(B) are hydrogen and C₁-C₆-alkyl; where the cyclic groups in R¹ and/or R^(a) may be substituted by one to four groups R^(b): R^(b) is halogen, cyano, hydroxyl, mercapto, nitro, NR^(A)R^(B), C₁-C₁₀-alkyl, C₁-C₆-haloalkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl or C₁-C₆-alkoxy; R³ is hydrogen, halogen, cyano, NR^(A)R^(B), hydroxyl, mercapto, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₃-C₈-cycloalkyl, C₁-C₆-alkoxy, C₁-C₆-alkylthio, C₃-C₈-cycloalkoxy, C₃-C₈-cycloalkylthio, carboxyl, formyl, C₁-C₁₀-alkylcarbonyl, C₁-C₁₀-alkoxycarbonyl, C₂-C₁₀-alkenyloxycarbonyl, C₂-C₁₀-alkynyloxycarbonyl, phenyl, phenoxy, phenylthio, benzyloxy, benzylthio, or C₁-C₆-alkyl-S(O)_(m)—; m is 0, 1 or 2; A is CR³ or N; and 2) at least one active compound II selected from the group consisting of: A) bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, enilconazole, epoxiconazole, fluquinconazole, fenbuconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, penconazole, propiconazole, prothioconazole, simeconazole, triadimefon, triadimenol, tebuconazole, tetraconazole, triticonazole, prochloraz, pefurazoate, imazalil, triflumizole, cyazofamid, benomyl, carbendazim, thiabendazole, fuberidazole, ethaboxam, etridiazole, hymexazole; B) azoxystrobin, dimoxystrobin, enestroburin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, trifloxystrobin, methyl (2-chloro-5-[1-(3-methylbenzyloxyimino)ethyl]benzyl)carbamate, methyl (2-chloro-5-[1-(6-methylpyridin-2-ylmethoxyimino)ethyl]benzyl)carbamate, methyl 2-(ortho-((2,5-dimethylphenyloxymethylene)phenyl)-3-methoxyacrylate; C) carboxin, benalaxyl, boscalid, fenhexamid, flutolanil, furametpyr, mepronil, metalaxyl, mefenoxam, ofurace, oxadixyl, oxycarboxin, penthiopyrad, thifluzamide, tiadinil, N-(4′-bromobiphenyl-2-yl)-4-difluoromethyl-2-methylthiazole-5-carboxamide, N-(4′-trifluoromethylbiphenyl-2-yl)-4-difluoromethyl-2-methylthiazole-5-carboxamide, N-(4′-chloro-3′-fluorobiphenyl-2-yl)-4-difluoromethyl-2-methylthiazole-5-carboxamide, N-(3′,4′-dichloro-4-fluorobiphenyl-2-yl)-3-difluoromethyl-1-methylpyrazole-4-carboxamide, N-(3′,4′-dichloro-5-fluorobiphenyl-2-yl)-3-difluoromethyl-1-methylpyrazole-4-carboxamide, 3,4-dichloro-N-(2-cyanophenyl)isothiazol-5-carboxamide, dimethomorph, flumorph; flumetover, fluopicolide (picobenzamid), zoxamide, carpropamid, diclocymet, mandipropamid; N-(2-{4-[3-(4-chlorophenyl)prop-2-ynyloxy]-3-methoxyphenyl}ethyl)-2-methanesulfonylamino-3-methylbutyramide, N-(2-{4-[3-(4-chlorophenyl)-prop-2-ynyloxy]-3-methoxyphenyl}ethyl)-2-ethanesulfonylamino-3-methylbutyramide; D) fluazinam, pyrifenox, bupirimate, cyprodinil, fenarimol, ferimzone, mepanipyrim, nuarimol, pyrimethanil triforine, fenpiclonil, fludioxonil aldimorph, dodemorph, fenpropimorph, tridemorph, fenpropidin, iprodione, procymidone, vinclozolin, famoxadone, fenamidone, octhilinone, probenazole, anilazine, diclomezine, pyroquilon, proquinazid, tricyclazole, amisulbrom, 5-chloro-7-(4-methylpiperidin-1-yl)-6-(2,4,6-trifluorophenyl)-[1,2,4]triazolo[1,5-a]pyrimidine, 2-butoxy-6-iodo-3-propylchromen-4-one, acibenzolar-5-methyl, captafol, captan, dazomet, folpet, fenoxanil, quinoxyfen, 3-[5-(4-chlorophenyl)-2,3-dimethylisoxazolidin-3-yl]pyridine; E) mancozeb, maneb, metam, metiram, ferbam, propineb, thiram, zineb, ziram, diethofencarb, iprovalicarb, flubenthiavalicarb, propamocarb, and methyl 3-(4-chlorophenyl)-3-(2-isopropoxycarbonylamino-3-methylbutyrylamino)propanoate; and F) dodine, iminoctadine, guazatine; kasugamycin, streptomycin, polyoxine, validamycin A; binapacryl, dinocap, dinobuton; dithianon, isoprothiolane; fentin salts; edifenphos, iprobenfos, fosetyl, fosetyl-aluminum, phosphorous acid and its salts, pyrazophos, tolclofos-methyl; chlorothalonil, dichlofluanid, flusulfamide, hexachlorobenzene, phthalide, pencycuron, quintozene, thiophanate-methyl, tolylfluanid; Bordeaux mixture, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, sulfur; cyflufenamid, cymoxanil, dimethirimol, ethirimol, furalaxyl, metrafenone, spiroxamine; prohexadione and its salts, trinexapac-ethyl, chlormequat, mepiquat-chloride, diflufenzopyr; wherein the azolopyrimidinylamine of formula I and the at least one active compound II of the mixture are present in a synergistically effective amount.
 9. The composition of claim 8, wherein the azolopyrimidinylamine of formula I is of the formula IA

wherein R¹ is C₃-C₁₂-alkyl, C₅-C₁₂-alkoxyalkyl, phenyl or phenyl-C₁-C₄-alkyl, where phenyl may be substituted by one to three groups R^(b); R² is C₁-C₁₂-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy-C₁-C₄-alkyl; R³ is hydrogen or NH₂.
 10. The composition of claim 8, wherein the azolopyrimidinylamine of formula I is selected from the group consisting of 6-(3,4-dichloro-phenyl)-5-methyl-[1,2,4]triazolo[1,5-a]pyrimidin-7-ylamine; 6-(4-tert-butylphenyl)-5-methyl-[1,2,4]triazolo[1,5-a]pyrimidin-7-ylamine; 5-methyl-6-(3,5,5-trimethyl-hexyl)-[1,2,4]triazolo[1,5-a]pyrimidin-7-ylamine; 5-methyl-6-octyl-[1,2,4]triazolo[1,5-a]pyrimidin-7-ylamine; 6-methyl-5-octyl-[1,2,4]triazolo[1,5-a]pyrimidin-7-ylamine; 6-ethyl-5-octyl-[1,2,4]triazolo[1,5-a]pyrimidin-7-ylamine; 5-ethyl-6-octyl-[1,2,4]triazolo[1,5-a]pyrimidin-7-ylamine; 5-ethyl-6-(3,5,5-trimethyl-hexyl)-[1,2,4]triazolo[1,5-a]pyrimidin-7-ylamine; 6-octyl-5-propyl-[1,2,4]triazolo[1,5-a]pyrimidin-7-ylamine; 5-methoxymethyl-6-octyl-[1,2,4]triazolo[1,5-a]pyrimidin-7-ylamine; 6-octyl-5-trifluormethyl-[1,2,4]triazolo[1,5-a]pyrimidin-7-ylamine and 5-trifluoromethyl-6-(3,5,5-trimethyl-hexyl)-[1,2,4]triazolo[1,5-a]pyrimidin-7-ylamine.
 11. The composition of claim 8, wherein the at least one active compound II is selected from the group A, C or E.
 12. The composition of claim 8, wherein the at least one active compound II is selected from the group B, D or F.
 13. The composition of claim 8, wherein the mixture comprises the azolopyrimidinylamine of formula I and two active compounds II, wherein each active compound II is independently selected from the group A, B, C, D, E or F.
 14. A method for controlling phytopathogenic harmful fungi comprising treating fungi, their habitat, or plants to be protected against fungal attack, soil or seed with an effective amount of 1) an azolopyrimidinylamine of formula I

wherein: R¹ is C₃-C₁₂-alkyl, C₂-C₁₂-alkenyl, C₅-C₁₂-alkoxyalkyl, C₃-C₆-cycloalkyl, phenyl or phenyl-C₁-C₄-alkyl; R² is C₁-C₁₂-alkyl, C₂-C₁₂-alkenyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy-C₁-C₄-alkyl; where the aliphatic chains in R¹ and/or R² may be substituted by one to four identical or different groups R^(a): R^(a) is halogen, cyano, hydroxyl, mercapto, C₁-C₁₀-alkyl, C₁-C₁₀-haloalkyl, C₃-C₈-cycloalkyl, C₂-C₁₀-alkenyl, C₂-C₁₀-alkynyl, C₁-C₆-alkoxy, C₁-C₆-alkylthio, C₁-C₆-alkoxy-C₁-C₆-alkyl or NR^(A)R^(B); R^(A), R^(B) are hydrogen and C₁-C₆-alkyl; where the cyclic groups in R¹ and/or R^(a) may be substituted by one to four groups R^(b): R^(b) is halogen, cyano, hydroxyl, mercapto, nitro, NR^(A)R^(B), C₁-C₁₀-alkyl, C₁-C₆-haloalkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl or C₁-C₆-alkoxy; R³ is hydrogen, halogen, cyano, NR^(A)R^(B), hydroxyl, mercapto, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₃-C₈-cycloalkyl, C₁-C₆-alkoxy, C₁-C₆-alkylthio, C₃-C₈-cycloalkoxy, C₃-C₈-cycloalkylthio, carboxyl, formyl, C₁-C₁₀-alkylcarbonyl, C₁-C₁₀-alkoxycarbonyl, C₂-C₁₀-alkenyloxycarbonyl, C₂-C₁₀-alkynyloxycarbonyl, phenyl, phenoxy, phenylthio, benzyloxy, benzylthio, or C₁-C₆-alkyl-S(O)_(m)—; m is 0, 1 or 2; A is CR³ or N; and 2) at least one active compound II selected from the group consisting of: A) bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, enilconazole, epoxiconazole, fluquinconazole, fenbuconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, penconazole, propiconazole, prothioconazole, simeconazole, triadimefon, triadimenol, tebuconazole, tetraconazole, triticonazole, prochloraz, pefurazoate, imazalil, triflumizole, cyazofamid, benomyl, carbendazim, thiabendazole, fuberidazole, ethaboxam, etridiazole, hymexazole; B) azoxystrobin, dimoxystrobin, enestroburin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, trifloxystrobin, methyl (2-chloro-5-[1-(3-methylbenzyloxyimino)ethyl]benzyl)carbamate, methyl (2-chloro-5-[1-(6-methylpyridin-2-ylmethoxyimino)ethyl]benzyl)carbamate, methyl 2-(ortho-((2,5-dimethylphenyloxymethylene)phenyl)-3-methoxyacrylate; C) carboxin, benalaxyl, boscalid, fenhexamid, flutolanil, furametpyr, mepronil, metalaxyl, mefenoxam, ofurace, oxadixyl, oxycarboxin, penthiopyrad, thifluzamide, tiadinil, N-(4′-bromobiphenyl-2-yl)-4-difluoromethyl-2-methylthiazole-5-carboxamide, N-(4′-trifluoromethylbiphenyl-2-yl)-4-difluoromethyl-2-methylthiazole-5-carboxamide, N-(4′-chloro-3′-fluorobiphenyl-2-yl)-4-difluoromethyl-2-methylthiazole-5-carboxamide, N-(3′,4′-dichloro-4-fluorobiphenyl-2-yl)-3-difluoromethyl-1-methylpyrazole-4-carboxamide, N-(3′,4′-dichloro-5-fluorobiphenyl-2-yl)-3-difluoromethyl-1-methylpyrazole-4-carboxamide, 3,4-dichloro-N-(2-cyanophenyl)isothiazol-5-carboxamide, dimethomorph, flumorph; flumetover, fluopicolide (picobenzamid), zoxamide, carpropamid, diclocymet, mandipropamid; N-(2-{4-[3-(4-chlorophenyl)prop-2-ynyloxy]-3-methoxyphenyl}ethyl)-2-methanesulfonylamino-3-methylbutyramide, N-(2-{4-[3-(4-chlorophenyl)-prop-2-ynyloxy]-3-methoxyphenyl}ethyl)-2-ethanesulfonylamino-3-methylbutyramide; D) fluazinam, pyrifenox, bupirimate, cyprodinil, fenarimol, ferimzone, mepanipyrim, nuarimol, pyrimethanil triforine, fenpiclonil, fludioxonil aldimorph, dodemorph, fenpropimorph, tridemorph, fenpropidin, iprodione, procymidone, vinclozolin, famoxadone, fenamidone, octhilinone, probenazole, anilazine, diclomezine, pyroquilon, proquinazid, tricyclazole, amisulbrom, 5-chloro-7-(4-methylpiperidin-1-yl)-6-(2,4,6-trifluorophenyl)-[1,2,4]triazolo[1,5-a]pyrimidine, 2-butoxy-6-iodo-3-propylchromen-4-one, acibenzolar-5-methyl, captafol, captan, dazomet, folpet, fenoxanil, quinoxyfen, 3-[5-(4-chlorophenyl)-2,3-dimethylisoxazolidin-3-yl]pyridine; E) mancozeb, maneb, metam, metiram, ferbam, propineb, thiram, zineb, ziram, diethofencarb, iprovalicarb, flubenthiavalicarb, propamocarb, and methyl 3-(4-chlorophenyl)-3-(2-isopropoxycarbonylamino-3-methylbutyrylamino)propanoate; and F) dodine, iminoctadine, guazatine; kasugamycin, streptomycin, polyoxine, validamycin A; binapacryl, dinocap, dinobuton; dithianon, isoprothiolane; fentin salts; edifenphos, iprobenfos, fosetyl, fosetyl-aluminum, phosphorous acid and its salts, pyrazophos, tolclofos-methyl; chlorothalonil, dichlofluanid, flusulfamide, hexachlorobenzene, phthalide, pencycuron, quintozene, thiophanate-methyl, tolylfluanid; Bordeaux mixture, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, sulfur; cyflufenamid, cymoxanil, dimethirimol, ethirimol, furalaxyl, metrafenone, spiroxamine; prohexadione and its salts, trinexapac-ethyl, chlormequat, mepiquat-chloride, diflufenzopyr; wherein the azolopyrimidinylamine of formula I and the at least one active compound II of the mixture are present in a synergistically effective amount; wherein the phytopathogenic harmful fungi are controlled.
 15. The method of claim 14, wherein the weight ratio of the azolopyrimidinylamine of formula I and the at least one active compound of formula II is from 100:1 to 1:100.
 16. The method of claim 14, wherein the azolopyrimidinylamine of formula I is of the formula IA

wherein R¹ is C₃-C₁₂-alkyl, C₅-C₁₂-alkoxyalkyl, phenyl or phenyl-C₁-C₄-alkyl, where phenyl may be substituted by one to three groups R^(b); R² is C₁-C₁₂-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy-C₁-C₄-alkyl; R³ is hydrogen or NH₂.
 17. The method of claim 14, wherein the azolopyrimidinylamine of formula I is selected from the group consisting of 6-(3,4-dichloro-phenyl)-5-methyl-[1,2,4]triazolo[1,5-a]pyrimidin-7-ylamine; 6-(4-tert-butylphenyl)-5-methyl-[1,2,4]triazolo[1,5-a]pyrimidin-7-ylamine; 5-methyl-6-(3,5,5-trimethyl-hexyl)-[1,2,4]triazolo[1,5-a]pyrimidin-7-ylamine; 5-methyl-6-octyl-[1,2,4]triazolo[1,5-a]pyrimidin-7-ylamine; 6-methyl-5-octyl-[1,2,4]triazolo[1,5-a]pyrimidin-7-ylamine; 6-ethyl-5-octyl-[1,2,4]triazolo[1,5-a]pyrimidin-7-ylamine; 5-ethyl-6-octyl-[1,2,4]triazolo[1,5-a]pyrimidin-7-ylamine; 5-ethyl-6-(3,5,5-trimethyl-hexyl)-[1,2,4]triazolo[1,5-a]pyrimidin-7-ylamine; 6-octyl-5-propyl-[1,2,4]triazolo[1,5-a]pyrimidin-7-ylamine; 5-methoxymethyl-6-octyl-[1,2,4]triazolo[1,5-a]pyrimidin-7-ylamine; 6-octyl-5-trifluormethyl-[1,2,4]triazolo[1,5-a]pyrimidin-7-ylamine and 5-trifluoromethyl-6-(3,5,5-trimethyl-hexyl)-[1,2,4]triazolo[1,5-a]pyrimidin-7-ylamine.
 18. The method of claim 14, wherein the azolopyrimidinylamine of formula I and the at least one active compound II are applied simultaneously, separately, or in succession.
 19. The method of claim 14, wherein the azolopyrimidinylamine of formula I and the at least one active compound II are applied in an amount of from 5 g/ha to 2000 g/ha.
 20. The method of claim 14, wherein the azolopyrimidinylamine of formula I and the at least one active compound II are applied in an amount of from 1 g to 1000 g/100 kg of seed.
 21. The method of claim 14, wherein harmful fungi from the class of Oomycetes are controlled.
 22. Seed, comprising a mixture of 1) an azolopyrimidinylamine of formula I

wherein: R¹ is C₃-C₁₂-alkyl, C₂-C₁₂-alkenyl, C₅-C₁₂-alkoxyalkyl, C₃-C₆-cycloalkyl, phenyl or phenyl-C₁-C₄-alkyl; R² is C₁-C₁₂-alkyl, C₂-C₁₂-alkenyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy-C₁-C₄-alkyl; where the aliphatic chains in R¹ and/or R² may be substituted by one to four identical or different groups R^(a): R^(a) is halogen, cyano, hydroxyl, mercapto, C₁-C₁₀-alkyl, C₁-C₁₀-haloalkyl, C₃-C₈-cycloalkyl, C₂-C₁₀-alkenyl, C₂-C₁₀-alkynyl, C₁-C₆-alkoxy, C₁-C₆-alkylthio, C₁-C₆-alkoxy-C₁-C₆-alkyl or NR^(A)R^(B); R^(A), R^(B) are hydrogen and C₁-C₆-alkyl; where the cyclic groups in R¹ and/or R^(a) may be substituted by one to four groups R^(b): R^(b) is halogen, cyano, hydroxyl, mercapto, nitro, NR^(A)R^(B), C₁-C₁₀-alkyl, C₁-C₆-haloalkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl or C₁-C₆-alkoxy; R³ is hydrogen, halogen, cyano, NR^(A)R^(B), hydroxyl, mercapto, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₃-C₈-cycloalkyl, C₁-C₆-alkoxy, C₁-C₆-alkylthio, C₃-C₈-cycloalkoxy, C₃-C₈-cycloalkylthio, carboxyl, formyl, C₁-C₁₀-alkylcarbonyl, C₁-C₁₀-alkoxycarbonyl, C₂-C₁₀-alkenyloxycarbonyl, C₂-C₁₀-alkynyloxycarbonyl, phenyl, phenoxy, phenylthio, benzyloxy, benzylthio, or C₁-C₆-alkyl-S(O)_(m)—; m is 0, 1 or 2; A is CR³ or N; and 2) at least one active compound II selected from the group consisting of: A) bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, enilconazole, epoxiconazole, fluquinconazole, fenbuconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, penconazole, propiconazole, prothioconazole, simeconazole, triadimefon, triadimenol, tebuconazole, tetraconazole, triticonazole, prochloraz, pefurazoate, imazalil, triflumizole, cyazofamid, benomyl, carbendazim, thiabendazole, fuberidazole, ethaboxam, etridiazole, hymexazole; B) azoxystrobin, dimoxystrobin, enestroburin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, trifloxystrobin, methyl (2-chloro-5-[1-(3-methylbenzyloxyimino)ethyl]benzyl)carbamate, methyl (2-chloro-5-[1-(6-methylpyridin-2-ylmethoxyimino)ethyl]benzyl)carbamate, methyl 2-(ortho-((2,5-dimethylphenyloxymethylene)phenyl)-3-methoxyacrylate; C) carboxin, benalaxyl, boscalid, fenhexamid, flutolanil, furametpyr, mepronil, metalaxyl, mefenoxam, ofurace, oxadixyl, oxycarboxin, penthiopyrad, thifluzamide, tiadinil, N-(4′-bromobiphenyl-2-yl)-4-difluoromethyl-2-methylthiazole-5-carboxamide, N-(4′-trifluoromethylbiphenyl-2-yl)-4-difluoromethyl-2-methylthiazole-5-carboxamide, N-(4′-chloro-3′-fluorobiphenyl-2-yl)-4-difluoromethyl-2-methylthiazole-5-carboxamide, N-(3′,4′-dichloro-4-fluorobiphenyl-2-yl)-3-difluoromethyl-1-methylpyrazole-4-carboxamide, N-(3′,4′-dichloro-5-fluorobiphenyl-2-yl)-3-difluoromethyl-1-methylpyrazole-4-carboxamide, 3,4-dichloro-N-(2-cyanophenyl)isothiazol-5-carboxamide, dimethomorph, flumorph; flumetover, fluopicolide (picobenzamid), zoxamide, carpropamid, diclocymet, mandipropamid; N-(2-{4-[3-(4-chlorophenyl)prop-2-ynyloxy]-3-methoxyphenyl}ethyl)-2-methanesulfonylamino-3-methylbutyramide, N-(2-{4-[3-(4-chlorophenyl)-prop-2-ynyloxy]-3-methoxyphenyl}ethyl)-2-ethanesulfonylamino-3-methylbutyramide; D) fluazinam, pyrifenox, bupirimate, cyprodinil, fenarimol, ferimzone, mepanipyrim, nuarimol, pyrimethanil triforine, fenpiclonil, fludioxonil aldimorph, dodemorph, fenpropimorph, tridemorph, fenpropidin, iprodione, procymidone, vinclozolin, famoxadone, fenamidone, octhilinone, probenazole, anilazine, diclomezine, pyroquilon, proquinazid, tricyclazole, amisulbrom, 5-chloro-7-(4-methylpiperidin-1-yl)-6-(2,4,6-trifluorophenyl)-[1,2,4]triazolo[1,5-a]pyrimidine, 2-butoxy-6-iodo-3-propylchromen-4-one, acibenzolar-5-methyl, captafol, captan, dazomet, folpet, fenoxanil, quinoxyfen, 3-[5-(4-chlorophenyl)-2,3-dimethylisoxazolidin-3-yl]pyridine; E) mancozeb, maneb, metam, metiram, ferbam, propineb, thiram, zineb, ziram, diethofencarb, iprovalicarb, flubenthiavalicarb, propamocarb, and methyl 3-(4-chlorophenyl)-3-(2-isopropoxycarbonylamino-3-methylbutyrylamino)propanoate; and F) dodine, iminoctadine, guazatine; kasugamycin, streptomycin, polyoxine, validamycin A; binapacryl, dinocap, dinobuton; dithianon, isoprothiolane; fentin salts; edifenphos, iprobenfos, fosetyl, fosetyl-aluminum, phosphorous acid and its salts, pyrazophos, tolclofos-methyl; chlorothalonil, dichlofluanid, flusulfamide, hexachlorobenzene, phthalide, pencycuron, quintozene, thiophanate-methyl, tolylfluanid; Bordeaux mixture, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, sulfur; cyflufenamid, cymoxanil, dimethirimol, ethirimol, furalaxyl, metrafenone, spiroxamine; prohexadione and its salts, trinexapac-ethyl, chlormequat, mepiquat-chloride, diflufenzopyr; wherein the azolopyrimidinylamine of formula I and the at least one active compound II of the mixture are present in a synergistically effective amount; in an amount of from 1 to 1000 g/100 kg of seed.
 23. The seed of claim 22, wherein the azolopyrimidinylamine of formula I is of the formula IA

wherein R¹ is C₃-C₁₂-alkyl, C₅-C₁₂-alkoxyalkyl, phenyl or phenyl-C₁-C₄-alkyl, where phenyl may be substituted by one to three groups R^(b); R² is C₁-C₁₂-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy-C₁-C₄-alkyl; R³ is hydrogen or NH₂.
 24. The seed of claim 22, wherein the azolopyrimidinylamine of formula I is selected from the group consisting of 6-(3,4-dichloro-phenyl)-5-methyl-[1,2,4]triazolo[1,5-a]pyrimidin-7-ylamine; 6-(4-tert-butylphenyl)-5-methyl-[1,2,4]triazolo[1,5-a]pyrimidin-7-ylamine; 5-methyl-6-(3,5,5-trimethyl-hexyl)-[1,2,4]triazolo[1,5-a]pyrimidin-7-ylamine; 5-methyl-6-octyl-[1,2,4]triazolo[1,5-a]pyrimidin-7-ylamine; 6-methyl-5-octyl-[1,2,4]triazolo[1,5-a]pyrimidin-7-ylamine; 6-ethyl-5-octyl-[1,2,4]triazolo[1,5-a]pyrimidin-7-ylamine; 5-ethyl-6-octyl-[1,2,4]triazolo[1,5-a]pyrimidin-7-ylamine; 5-ethyl-6-(3,5,5-trimethyl-hexyl)-[1,2,4]triazolo[1,5-a]pyrimidin-7-ylamine; 6-octyl-5-propyl-[1,2,4]triazolo[1,5-a]pyrimidin-7-ylamine; 5-methoxymethyl-6-octyl-[1,2,4]triazolo[1,5-a]pyrimidin-7-ylamine; 6-octyl-5-trifluormethyl-[1,2,4]triazolo[1,5-a]pyrimidin-7-ylamine and 5-trifluoromethyl-6-(3,5,5-trimethyl-hexyl)-[1,2,4]triazolo[1,5-a]pyrimidin-7-ylamine.
 25. The seed of claim 22, wherein the at least one active compound II is selected from the group A, C or E.
 26. The seed of claim 22, wherein the at least one active compound II is selected from the group B, D or F.
 27. The seed of claim 22, wherein the mixture comprises the azolopyrimidinylamine of formula I and two active compounds II, wherein each active compound II is independently selected from the group A, B, C, D, E or F.
 28. A process for preparing a composition comprising contacting liquid or solid carriers with a mixture of 1) an azolopyrimidinylamine of formula I

wherein: R¹ is C₃-C₁₂-alkyl, C₂-C₁₂-alkenyl, C₅-C₁₂-alkoxyalkyl, C₃-C₆-cycloalkyl, phenyl or phenyl-C₁-C₄-alkyl; R² is C₁-C₁₂-alkyl, C₂-C₁₂-alkenyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy-C₁-C₄-alkyl; where the aliphatic chains in R¹ and/or R² may be substituted by one to four identical or different groups R^(a): R^(a) is halogen, cyano, hydroxyl, mercapto, C₁-C₁₀-alkyl, C₁-C₁₀-haloalkyl, C₃-C₈-cycloalkyl, C₂-C₁₀-alkenyl, C₂-C₁₀-alkynyl, C₁-C₆-alkoxy, C₁-C₆-alkylthio, C₁-C₆-alkoxy-C₁-C₆-alkyl or NR^(A)R^(B); R^(A), R^(B) are hydrogen and C₁-C₆-alkyl; where the cyclic groups in R¹ and/or R^(a) may be substituted by one to four groups R^(b): R^(b) is halogen, cyano, hydroxyl, mercapto, nitro, NR^(A)R^(B), C₁-C₁₀-alkyl, C₁-C₆-haloalkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl or C₁-C₆-alkoxy; R³ is hydrogen, halogen, cyano, NR^(A)R^(B), hydroxyl, mercapto, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₃-C₈-cycloalkyl, C₁-C₆-alkoxy, C₁-C₆-alkylthio, C₃-C₈-cycloalkoxy, C₃-C₈-cycloalkylthio, carboxyl, formyl, C₁-C₁₀-alkylcarbonyl, C₁-C₁₀-alkoxycarbonyl, C₂-C₁₀-alkenyloxycarbonyl, C₂-C₁₀-alkynyloxycarbonyl, phenyl, phenoxy, phenylthio, benzyloxy, benzylthio, or C₁-C₆-alkyl-S(O)_(m)—; m is 0, 1 or 2; A is CR³ or N; and 2) at least one active compound II selected from the group consisting of: A) bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, enilconazole, epoxiconazole, fluquinconazole, fenbuconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, penconazole, propiconazole, prothioconazole, simeconazole, triadimefon, triadimenol, tebuconazole, tetraconazole, triticonazole, prochloraz, pefurazoate, imazalil, triflumizole, cyazofamid, benomyl, carbendazim, thiabendazole, fuberidazole, ethaboxam, etridiazole, hymexazole; B) azoxystrobin, dimoxystrobin, enestroburin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, trifloxystrobin, methyl (2-chloro-5-[1-(3-methylbenzyloxyimino)ethyl]benzyl)carbamate, methyl (2-chloro-5-[1-(6-methylpyridin-2-ylmethoxyimino)ethyl]benzyl)carbamate, methyl 2-(ortho-((2,5-dimethylphenyloxymethylene)phenyl)-3-methoxyacrylate; C) carboxin, benalaxyl, boscalid, fenhexamid, flutolanil, furametpyr, mepronil, metalaxyl, mefenoxam, ofurace, oxadixyl, oxycarboxin, penthiopyrad, thifluzamide, tiadinil, N-(4′-bromobiphenyl-2-yl)-4-difluoromethyl-2-methylthiazole-5-carboxamide, N-(4′-trifluoromethylbiphenyl-2-yl)-4-difluoromethyl-2-methylthiazole-5-carboxamide, N-(4′-chloro-3′-fluorobiphenyl-2-yl)-4-difluoromethyl-2-methylthiazole-5-carboxamide, N-(3′,4′-dichloro-4-fluorobiphenyl-2-yl)-3-difluoromethyl-1-methylpyrazole-4-carboxamide, N-(3′,4′-dichloro-5-fluorobiphenyl-2-yl)-3-difluoromethyl-1-methylpyrazole-4-carboxamide, 3,4-dichloro-N-(2-cyanophenyl)isothiazol-5-carboxamide, dimethomorph, flumorph; flumetover, fluopicolide (picobenzamid), zoxamide, carpropamid, diclocymet, mandipropamid; N-(2-{4-[3-(4-chlorophenyl)prop-2-ynyloxy]-3-methoxyphenyl}ethyl)-2-methanesulfonylamino-3-methylbutyramide, N-(2-{4-[3-(4-chlorophenyl)-prop-2-ynyloxy]-3-methoxyphenyl}ethyl)-2-ethanesulfonylamino-3-methylbutyramide; D) fluazinam, pyrifenox, bupirimate, cyprodinil, fenarimol, ferimzone, mepanipyrim, nuarimol, pyrimethanil triforine, fenpiclonil, fludioxonil aldimorph, dodemorph, fenpropimorph, tridemorph, fenpropidin, iprodione, procymidone, vinclozolin, famoxadone, fenamidone, octhilinone, probenazole, anilazine, diclomezine, pyroquilon, proquinazid, tricyclazole, amisulbrom, 5-chloro-7-(4-methylpiperidin-1-yl)-6-(2,4,6-trifluorophenyl)-[1,2,4]triazolo[1,5-a]pyrimidine, 2-butoxy-6-iodo-3-propylchromen-4-one, acibenzolar-5-methyl, captafol, captan, dazomet, folpet, fenoxanil, quinoxyfen, 3-[5-(4-chlorophenyl)-2,3-dimethylisoxazolidin-3-yl]pyridine; E) mancozeb, maneb, metam, metiram, ferbam, propineb, thiram, zineb, ziram, diethofencarb, iprovalicarb, flubenthiavalicarb, propamocarb, and methyl 3-(4-chlorophenyl)-3-(2-isopropoxycarbonylamino-3-methylbutyrylamino)propanoate; and F) dodine, iminoctadine, guazatine; kasugamycin, streptomycin, polyoxine, validamycin A; binapacryl, dinocap, dinobuton; dithianon, isoprothiolane; fentin salts; edifenphos, iprobenfos, fosetyl, fosetyl-aluminum, phosphorous acid and its salts, pyrazophos, tolclofos-methyl; chlorothalonil, dichlofluanid, flusulfamide, hexachlorobenzene, phthalide, pencycuron, quintozene, thiophanate-methyl, tolylfluanid; Bordeaux mixture, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, sulfur; cyflufenamid, cymoxanil, dimethirimol, ethirimol, furalaxyl, metrafenone, spiroxamine; prohexadione and its salts, trinexapac-ethyl, chlormequat, mepiquat-chloride, diflufenzopyr; wherein the azolopyrimidinylamine of formula I and the at least one active compound II of the mixture are present in a synergistically effective amount; wherein a composition is prepared. 